CN106496395B - A method of utilizing snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer composite material - Google Patents
A method of utilizing snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer composite material Download PDFInfo
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Abstract
The present invention discloses a kind of method using snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer composite material, and steps are as follows: 1) preparing snowman Janus composite particles；2) the snowman Janus composite particles of imidazolinyl modification are prepared；3) the snow figure type Janus composite particles of Ionic Liquid Modified are prepared；4) High Internal Phase Emulsion is prepared；5) poly- High Internal Phase Emulsion is prepared, with the water phase in ethyl alcohol removal High Internal Phase Emulsion, in 60-70 DEG C of vacuum drying 12-14h, the porous polymer composite material i.e. ion liquid functionalization through-hole structure porous polymer composite material of ion liquid functionalization through-hole structure is obtained.Preparation method of the present invention is simple, and raw material is easy to get, and can be prepared on a large scale, and the prepared polymer porous material permeability with ionic liquid base is good, can be used in the application of catalysis, absorption etc..
Description
Technical field
Snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer is utilized the present invention relates to a kind of
The method of composite material.
Background technique
Porous material due to for example lower density of its unique physical property, big specific surface area, high porosity thus
So that this kind of material has extensively in the fields such as liquid chromatogram, mass transfer, absorption and separation, surface catalysis, biomedical engineering
General application value.And in these porous materials, polymer porous material is since its is at low cost, easy processing, corrosion-resistant etc. excellent
Point causes the great interest of researcher.
High Internal Phase Emulsion template is answered extensively due to the features such as aperture of porous material of preparation is controllable and easy to operate
With.Since the internal phase volume score of High Internal Phase Emulsion is higher than 75%, in order to which the High Internal Phase Emulsion for obtaining stable usually needs to be added
The up to surfactant of continuous phase content 20-30%, so that the degradation of the porous material obtained after polymerization, simultaneously
The toxicity of surfactant can impact environment and human health.For conventional surfactant stabilising system,
It is irreversible in oil-water two-phase interfaces that polymer porous material particle emulsifying agents are prepared using Pickering High Internal Phase Emulsion as template
The dosage of solid particle that makes of absorption behavior it is less, and emulsifier particle eventually stays in Polymer Systems and forms composite wood
Material, so that the mechanical property of polymer porous material significantly improves.However tool often can only obtain as stabilizer using solid particle
There is the polymer large pore material of hole-closing structure, significantly limits porous polymer in the application of various fields.Therefore, preparation tool
The poly- Pickering High Internal Phase Emulsion of through-hole structure is a very big challenge.
The surface wettability of solid particle is to determine whether it can be used to an important factor for preparing lotion, institute in the present invention
The snowman Janus granule-morphology used is uniform (500nm), can construct the oil hydrosol system of high stability and be easy to large quantities of
Amount preparation；On the other hand, it is silica which, which is one end, and the hydrophobic polystyrene polymeric of the other end can modify two
Silica changes the surface wettability of entire material and assigns its certain functionality.The study found that ionic liquid has low wave
The features such as hair property, dissolubility be good, environmentally protective, electrochemical window mouth width and be widely used in organic reaction, catalysis, separation electrification
Learn etc..But at present ionic liquid there are price compared with high, dosage, big, catalyst is not readily separated purification the disadvantages of；Furthermore
For hardly possible volatilization or nonvolatile reactant and product, separating ionic liquid is also very cumbersome with reaction mixture, by ionic liquid
Body forms solid-loaded ionic-liquid by the way that chemical bonding mode is immobilized.Heterogeneous catalysis is easy to by this solid-loaded ionic-liquid
Separation is combined with ionic liquid homogeneous catalysis characteristic, and excellent catalytic performance is shown in a large amount of organic syntheses.Base
In this, by imidazolinyl silane reagent it is terminal modified to silica one after can introduce ionic liquid base, by ionic liquid supported
On Janus material.Meanwhile Janus particle surface profit is adjusted in the long alkyl chains of alkyl halide used in ionic liquid process
It is moist.With the particle stabilized High Internal Phase Emulsion of the snowman Janus of ionic liquid base modification, solid particle is stayed in after polymerization reaction
So that polymeric inner hole surface is contained ionic liquid base on porous material, plays it by simple ion and exchange its performance of adjusting
The characteristics of.To extend porous polymer composite material absorption, in terms of potential application.
Summary of the invention
The present invention provides a kind of utilization snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer
The method of composite material, use it is nontoxic modified after snowman Janus particle for the emulsifier of Pickering High Internal Phase Emulsion,
It polymerize to obtain polymer porous material by the emulsion template.
The technical solution adopted by the present invention are as follows:
It is a kind of using snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer composite material
Method, steps are as follows:
1) snowman Janus composite particles are prepared
It takes polystyrene hollow ball to be dispersed in water to obtain polystyrene aqueous solution, adjusts the pH=8- of polystyrene aqueous solution
10, stirring forms seed emulsion at 60-70 DEG C；By 3- (methacryloxypropyl) propyl trimethoxy silicane, the mistake of 1.0wt%
Potassium sulfate solution, neopelex ultrasonic disperse in water, are allowed to form monomer emulsions；By monomer emulsions in 30-
It is slowly added dropwise in 40 minutes into seed emulsion, reaction carries out at 70-80 DEG C；It will be centrifuged resulting precipitating after reaction, use
Water, ethanol washing, centrifuge separation, and after being dried in vacuo 12-14h, obtain white powder, i.e. snowman Janus composite particles；
2) the snowman Janus composite particles of imidazolinyl modification are prepared
Snowman Janus composite particles ultrasound is allowed to dispersion in ethanol, adjusts the pH=8.0-9.0 of solution, then
Imidazolinyl triethoxysilane is added, return stirring 72-80h will be centrifuged resulting precipitating after reaction, and be washed with water
It washs, is centrifugated, and obtain white powder, i.e., snowman Janus compound of imidazolinyl modification after being dried in vacuo 12-14h
Grain；
3) the snow figure type Janus composite particles of Ionic Liquid Modified are prepared
The snow figure type composite particles for taking imidazolinyl to modify, ultrasound are allowed to dispersion in ethanol, add alkyl halide, then
The back flow reaction 72-80h at 80-90 DEG C, will be centrifuged resulting precipitating after reaction, be washed with water, centrifuge separation, and vacuum
White powder, i.e. the snowman Janus composite particles of Ionic Liquid Modified are obtained after dry 12-14h；
4) High Internal Phase Emulsion is prepared
Take styrene and divinylbenzene that in centrifuge tube, benzoyl peroxide, ultrasonic 20-30min is added as oil phase
Afterwards, then by the snow figure type Janus composite particles ultrasonic disperse of Ionic Liquid Modified it is added portionwise in oily phase, then into centrifuge tube
Water phase, acutely oscillation forms water-in-oil type High Internal Phase Emulsion；
5) poly- High Internal Phase Emulsion is prepared
It will be centrifuged the seal of tube, 12h is reacted at 80 DEG C, after reaction, remove the water phase in High Internal Phase Emulsion with ethyl alcohol,
In 60-70 DEG C of vacuum drying 12-14h, polyalcohol stephanoporate composite material of the ion liquid functionalization with through-hole structure is obtained i.e.
Ion liquid functionalization through-hole polyalcohol stephanoporate composite material.
The method, the middle NH with 28wt% of step 1)3·H2The pH=8-10 of O adjusting solution.
The method, 3- (methacryloxypropyl) propyl trimethoxy silicane in step 1), the potassium peroxydisulfate of 1.0wt%
Aqueous solution, the neopelex proportion of 1:1:0.01 in mass ratio feed intake.
The method, the matter liquid mg/ml ratio of snowman Janus composite particles and ethyl alcohol is 10:3 in step 2)；Snowman
The mass ratio of shape Janus composite particles and imidazolinyl triethoxysilane is 1:10.
The method, the snow figure type composite particles of imidazolinyl modification and the matter liquid mg/ml ratio of ethyl alcohol are in step 3)
2:1；The snow figure type composite particles of imidazolinyl modification and the matter liquid mg/ml ratio of alkyl halide are 20:1.
The method, alkyl halide is bromoalkane or alkyl chloride in step 3)；The bromoalkane is bromination of n-butane, bromo
Normal octane or bromododecane；The alkyl chloride is chloro-normal butane, n-octyl chloride or chlorinated dodecane.
The method, the volume ratio of styrene and divinylbenzene is 3:1-1:3 in step 4)；Benzoyl peroxide accounts for
The 0.5-2% of oily phase quality.
Water phase is added portionwise in step 4), the water phase of 0.2-0.4ml, the height are specially added every time for the method
Water phase volume fraction is 80-85.7% in internal phase emulsions.
The invention has the following advantages: the present invention is emulsifier using snowman Janus particle, prepare with phase in height
Lotion is the porous material of the through-hole polymer of template.Snowman Janus particulate silica one end is introduced into ionic liquid base,
And be scattered in styrene-divinylbenzene oil phase, initiator is added, water phase is added portionwise, is acutely formed after oscillation steady
Fixed water-in-oil type High Internal Phase Emulsion obtains compound with ion liquid functionalization through-hole polyalcohol stephanoporate by temperature reaction
Material.Preparation method of the present invention is simple, and raw material is easy to get, and can be prepared on a large scale, and prepared is porous with ionic liquid base
Polymer composites permeability is good, can be used in the application of catalysis, absorption etc..
Detailed description of the invention
Fig. 1 is snowman Janus composite particles FT-IR figure.A is original snowman Janus particle FT-IR figure；B imidazoline
Snowman Janus composite particles FT-IR figure after base modification.
Fig. 2 is that the SEM of snowman Janus particle schemes.
Fig. 3 is Br-The SEM of base ionic liquid snow figure type Janus composite particles schemes.
Fig. 4 is the SEM figure of ion liquid functionalization through-hole structure porous polymer composite A prepared by embodiment 1.
The SEM figure that Fig. 5 is ion liquid functionalization through-hole structure porous polymer composite material B prepared by embodiment 2.
The SEM figure that Fig. 6 is ion liquid functionalization through-hole structure porous polymer composite material C prepared by embodiment 3.
Fig. 7 is test High Internal Phase Emulsion stability diagram.
Fig. 8 is a monolith ion liquid functionalization through-hole structure porous polymer composite A of preparation.
Specific embodiment
Embodiment 1 is a kind of multiple using snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer
The method of condensation material
Steps are as follows:
1) snowman Janus composite particles are prepared
It takes 1g polystyrene hollow ball to be dispersed in 20g water, a certain amount of NH is then added3·H2O (28wt%) adjusts molten
The pH=8 of liquid, stirring forms seed emulsion at 70 DEG C.Again by 2g 3- (methacryloxypropyl) propyl trimethoxy silicane
(MPS), the persulfate aqueous solution (KPS) of 2g 1.0wt%, 0.02g neopelex (SDS) ultrasonic disperse is in 10g
In water, it is allowed to form monomer emulsions.Then monomer emulsions are slowly added dropwise into seed emulsion in 30 minutes, are reacted at 70 DEG C
It carries out.Resulting precipitating will be centrifuged after reaction, with water, ethyl alcohol is washed three times, be centrifugated and be dried in vacuo after 12h obtain it is white
Color powder, i.e. snowman Janus composite particles.
2) the snowman Janus composite particles of imidazolinyl modification are prepared
Take 100mg snowman Janus composite particles in a round bottom flask, ultrasound is allowed to be dispersed in 30ml ethyl alcohol, is added
A certain amount of NH3·H2O (28wt%) then adds 1g imidazolinyl triethoxysilane to adjust the pH=8.0 of solution
(IZPES), return stirring 72h.It will be centrifuged resulting precipitating after reaction, be washed with water three times, be centrifugated and be dried in vacuo
White powder, i.e. the snowman Janus composite particles of imidazolinyl modification are obtained after 12h.
3) Br is prepared-Base ionic liquid snowman Janus composite particles
The snowman composite particles for taking 100mg imidazolinyl to modify, ultrasound are allowed to be dispersed in 50ml ethyl alcohol, add
5ml bromination of n-butane, then the back flow reaction 72h at 80 DEG C.It will be centrifuged resulting precipitating after reaction, be washed with water three times,
It is centrifugated and obtains white powder, i.e. Br after being dried in vacuo 12h-Base ionic liquid snowman Janus composite particles.
4) High Internal Phase Emulsion is prepared
Take styrene with divinylbenzene as the mutually total 0.4ml (V of oilStyrene=0.3ml, VDivinylbenzene=0.1ml) and it is certain
The benzoyl peroxide (BPO) (BPO account for oily phase quality 1.25%) of amount is in centrifuge tube, after ultrasonic 20min, then by emulsifier
(the Br of the bromination of n-butane modification of 25mg-Base ionic liquid snowman Janus composite particles) ultrasonic disperse is in oily phase, in batches
Water phase (water phase of 0.2-0.4ml is added every time) is added, acutely oscillation forms water-in-oil type High Internal Phase Emulsion.Water phase volume fraction
For 80%-85.7%.
5) poly- High Internal Phase Emulsion is prepared
It will be centrifuged the seal of tube, react 12h at 80 DEG C, to make the monomer polymerization in continuous phase, after reaction, use second
Water phase in alcohol removal High Internal Phase Emulsion is utilized the ion of snowman Janus particle preparation in 60 DEG C of vacuum drying 12h
Liquid functional through-hole polyalcohol stephanoporate composite material, that is, ion liquid functionalization through-hole polyalcohol stephanoporate composite A.
Embodiment 2 is a kind of multiple using snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer
The method of condensation material
Bromination of n-butane in 1 step 3) of embodiment is only substituted for n-octane bromide, emulsifier in step 4) is changed
At the Br of the n-octane bromide ionic liquid of 15mg-Base ionic liquid snowman Janus composite particles.Finally obtained ionic liquid
Body function through-hole polyalcohol stephanoporate composite material B.
Embodiment 3 is a kind of multiple using snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer
The method of condensation material
Bromination of n-butane in 1 step 3) of embodiment is only substituted for bromododecane, emulsifier in step 4) is changed
At the Br of the bromododecane ionic liquid of 10mg-Base ionic liquid snowman Janus composite particles.It is final to obtain ionic liquid
Functionalization through-hole structure porous polymer composite material C.
Interpretation of result
Fig. 1 is snowman Janus composite particles FT-IR figure.A is original snowman Janus particle FT-IR figure；B imidazoline
Snowman Janus composite particles FT-IR figure after base modification.As shown in Figure 1,1663cm-The absorption peak at place belongs to imidazoline
The characteristic peak of base illustrates that imidazolinyl is successfully modified in snowman Janus particulate silica one end.
Fig. 2 is that the SEM of snowman Janus particle schemes.As shown in Figure 2, snowman Janus granule-morphology is uniform, and partial size is big
About 500nm.
Fig. 3 is Br-The SEM of base ionic liquid snow figure type Janus composite particles schemes.From the figure 3, it may be seen that imidazolinyl snowman
For Janus particle compared to the particle before modification both topographically there is no variation, partial size is still about 500nm.
Fig. 4 is the ion liquid functionalization through-hole polyalcohol stephanoporate composite material of 1 snowman Janus particle preparation of embodiment
The SEM of A schemes (VSTY=0.3ml, VDVB=0.1ml, VWater=2.4ml, mEmulsifier=25mg, VWater%=85.7%, emulsifier are bromos
The Br of normal butane ionic liquid-Base snowman Janus particle).As shown in Figure 4, with the Br of bromination of n-butane ionic liquid-
It is template that base snowman Janus particle, which is the stable High Internal Phase Emulsion of emulsifier, successfully prepares the polymerization with through-hole structure
Object is composite porous, and aperture is 100-400 μm, and through-hole aperture size is 20-30 μm.
The SEM that Fig. 5 is ion liquid functionalization through-hole polyalcohol stephanoporate composite material B prepared by embodiment 2 schemes (VSTY=
0.3ml, VDVB=0.1ml, VWater=2.4ml, mEmulsifier=15mg, VWater%=85.7%, emulsifier are n-octane bromide ionic liquids
The Br of change-Base snowman Janus particle).As shown in Figure 5, with the Br of n-octane bromide ionic liquid-Base snowman Janus
It is template that grain, which is the stable High Internal Phase Emulsion of emulsifier, successfully prepares the polyalcohol stephanoporate composite material with through-hole structure,
Aperture is 200-400 μm, and through-hole aperture size is 40-70 μm.
The SEM figure that Fig. 6 is ion liquid functionalization through-hole structure porous polymer composite material C prepared by embodiment 3
(VSTY=0.3ml, VDVB=0.1ml, VWater=2.4ml, mEmulsifier=10mg, VWater%=85.7%, emulsifier be bromododecane from
The Br of sub- fluidization-Base snowman Janus particle).It will be appreciated from fig. 6 that with the Br of bromododecane ionic liquid-Base snowman
Janus particle is that the stable High Internal Phase Emulsion of emulsifier is template, successfully prepares the polyalcohol stephanoporate material with through-hole structure
Material, macropore diameter are 250-400 μm, and through-hole aperture size is 40-60 μm.Emulsifier needed for comparison A, B, C can be seen that
The long alkyl chains of ionic liquid increase, and the hydrophobicity of Janus particle increases, and required emulsifier is reduced.
Fig. 7 is the High Internal Phase Emulsion stability test figure (V of 1 step 4) of embodiment preparationSTY=0.3ml, VDVB=0.1ml,
VWater80%)=1.6ml, water phase volume fraction are.As shown in Figure 7, as the increase of water phase volume forms the very big height of viscosity
Internal phase emulsions.After being inverted 72h, lotion does not also flow.
Fig. 8 is a monolith ion liquid functionalization through-hole structure porous polymer composite wood of 1 step 4) of embodiment preparation
Expect A.As shown in Figure 8, porous polymer composite shapes are cylinder, a length of 2.3cm, diameter 1cm.
Claims (8)
1. a kind of side using snowman Janus particle preparation ion liquid functionalization through-hole structure porous polymer composite material
Method, which is characterized in that steps are as follows:
1) snowman Janus composite particles are prepared
It takes polystyrene hollow ball to be dispersed in water to obtain polystyrene aqueous solution, adjusts the pH=8-10 of polystyrene aqueous solution,
Stirring forms seed emulsion at 60-70 DEG C；By 3- (methacryloxypropyl) propyl trimethoxy silicane, the over cure of 1.0wt%
Sour aqueous solutions of potassium, neopelex ultrasonic disperse in water, are allowed to form monomer emulsions；By monomer emulsions in 30-40
It is slowly added dropwise in minute into seed emulsion, reaction carries out at 70-80 DEG C；It will be centrifuged resulting precipitating after reaction, with water,
Ethanol washing, centrifuge separation, and after being dried in vacuo 12-14h, obtain white powder, i.e. snowman Janus composite particles；
2) the snowman Janus composite particles of imidazolinyl modification are prepared
Snowman Janus composite particles ultrasound is allowed to dispersion in ethanol, adjusts the pH=8.0-9.0 of solution, is then added again
Entering imidazolinyl triethoxysilane, return stirring 72-80h will be centrifuged resulting precipitating after reaction, be washed with water, from
Heart separation, and white powder, i.e. the snowman Janus composite particles of imidazolinyl modification are obtained after being dried in vacuo 12-14h；
3) the snow figure type Janus composite particles of Ionic Liquid Modified are prepared
The snow figure type composite particles for taking imidazolinyl to modify, ultrasound are allowed to dispersion in ethanol, add alkyl halide, then exist
Back flow reaction 72-80h at 80-90 DEG C, will be centrifuged resulting precipitating after reaction, be washed with water, centrifuge separation, and vacuum is dry
White powder, i.e. the snowman Janus composite particles of Ionic Liquid Modified are obtained after dry 12-14h；
4) High Internal Phase Emulsion is prepared
It takes styrene and divinylbenzene as oil mutually in centrifuge tube, is added benzoyl peroxide, after ultrasonic 20-30min, then
By the snow figure type Janus composite particles ultrasonic disperse of Ionic Liquid Modified in oily phase, then water phase is added portionwise into centrifuge tube,
Acutely oscillation forms water-in-oil type High Internal Phase Emulsion；
5) poly- High Internal Phase Emulsion is prepared
It will be centrifuged the seal of tube, 12h is reacted at 80 DEG C, after reaction, remove the water phase in High Internal Phase Emulsion with ethyl alcohol,
60-70 DEG C of vacuum drying 12-14h, obtain ion liquid functionalization with through-hole structure polyalcohol stephanoporate composite material i.e. from
Sub- liquid functional through-hole polyalcohol stephanoporate composite material.
2. the method as described in claim 1, which is characterized in that with the NH of 28wt% in step 1)3·H2The pH of O adjusting solution
=8-10.
3. the method as described in claim 1, which is characterized in that 3- (methacryloxypropyl) propyl trimethoxy silicon in step 1)
Alkane, the persulfate aqueous solution of 1.0wt%, the neopelex proportion of 1:1:0.01 in mass ratio feed intake.
4. the method as described in claim 1, which is characterized in that the matter of snowman Janus composite particles and ethyl alcohol in step 2)
Liquid mg/ml ratio is 10:3；The mass ratio of snowman Janus composite particles and imidazolinyl triethoxysilane is 1:10.
5. the method as described in claim 1, which is characterized in that in step 3) imidazolinyl modify snow figure type composite particles with
The matter liquid mg/ml ratio of ethyl alcohol is 2:1；The snow figure type composite particles of imidazolinyl modification and the matter liquid mg/ml ratio of alkyl halide are 20:
1。
6. the method as described in claim 1, which is characterized in that alkyl halide is bromoalkane or alkyl chloride in step 3)；The bromine
It is bromination of n-butane, n-octane bromide or bromododecane for alkane；The alkyl chloride is chloro-normal butane, n-octyl chloride or chlorine
For dodecane.
7. the method as described in claim 1, which is characterized in that the volume ratio of styrene and divinylbenzene is 3 in step 4):
1-1:3；Benzoyl peroxide accounts for the 0.5-2% of oily phase quality.
8. the method as described in claim 1, which is characterized in that water phase is added portionwise in step 4), is specially added every time
The water phase of 0.2-0.4ml, water phase volume fraction is 80-85.7% in the High Internal Phase Emulsion.
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| Interconnected Macroporous Polymers Synthesized from Silica Particle Stabilized High Internal Phase Emulsions;Xianhua Zheng，et al;《Macromolecules》;20140924;第47卷;第6847-6855页 |
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