CN103992425B - A kind of method that macropore solid acid catalyst is prepared in pickering emulsion polymerization - Google Patents
A kind of method that macropore solid acid catalyst is prepared in pickering emulsion polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of method that macropore solid acid catalyst is prepared in pickering emulsion polymerization, belong to technical field of environment function material preparation, by hydrolytic condensation synthetic silica particle, and use γ-methacryloxypropyl trimethoxy silane to be modified strengthening its hydrophobicity to it, then Span 80 in varing proportions and hydrophobic silicon ball particle are used as double; two emulsifying agent, have synthesized the pik woods High Internal Phase Emulsion material of the polymerization of a series of macropore, acid function.By scanning electron microscope, Fourier-infrared chromatography, ammonia temperature programmed desorption and the X-ray photoelectron spectroscopic analysis character of this material.At ambient pressure, cellulose becomes 5 hydroxymethyl furfural with 1-ethyl-3-methylimidazole chloride salt ions liquid for solvent conversion, obtains medium to good productivity, have studied the catalysis of this material activity.This material has very easily circulated after at least four times, activity not very big losing.
Description
Technical field
The present invention relates to a kind of method that macropore solid acid catalyst is prepared in pickering emulsion polymerization, belong to technical field of environment function material preparation.
Background technology
Along with the minimizing of fossil fuel reserves, people extremely pay close attention to abundant reproducible cellulose resource and go to replace Fossil fuel.In the use that cellulose produces fuel, one-step synthesis method 5 hydroxymethyl furfural is a very important step.5 hydroxymethyl furfural can very easily change into the bio-fuel of the furans of energy substitute fossil fuels and chemicals by condensation and hydrogenation reduction.Such as, 5 hydroxymethyl furfural can generate 2,5-dimethyl furans by hydrogenating reduction, and it is a kind of potentiality fuel also higher than ethanol energy density.Can be widely used in synthetic polymer from the 2,5-diformyl furan obtained of 5 hydroxymethyl furfural and 2,5-dihydroxymethyl furan.
In recent years, people with various acid be used as catalyst go research cellulose convert 5 hydroxymethyl furfural.Using goes catalytic degradation cellulose can obtain the 5 hydroxymethyl furfural that productivity is very high as the such homogeneous acid catalyst of hydrochloric acid and organic acid, but has disadvantages that in such a situa-tion, such as easy etching apparatus, by-product is many, separate difficulty, contaminated environment, the toxicity to human body.Along with the enhancing of environmental protection consciousness, people accelerate to use heterogeneous acidic catalyst especially solid acid to go degraded cellulose to obtain 5 hydroxymethyl furfural because their environmental protection, better circulate, can be easily separated, not corrosive equipment.Solid acid catalyst is widely used in various acid catalyzed reaction, in the solid catalyst of the fixing liquid acid of solid, zeolite, sulfide, natural clay mineral, ion exchange resin, heteropoly acid, oxide, solid super-strong acid, slaine, sulfonation carbon-based solid acid and polymer-matrix these types of solid acid, the polymer-matrix solid acid catalyst of the catalytic effect that density is little and outstanding is applied very active.Along with going deep into of people's understanding, it has been found that the acidic resins of perfluorosulfonic acid type are that the solid acid synthesizing the hydrophobic network structure of heat-flash stability provides correct direction, but, hole is lacked and the little application that have impact on as effective acid catalyst of specific surface area.
Because porous catalyst specific surface area is big, reaction condition is gentle, excellent catalytic effect, environmental friendliness, circulating effect are good, these advantages of instrument easily and are not corroded in separation, them are allowed to be widely used in field of catalytic reactions.But, reagent is had certain restriction by the porous catalyst having substantial amounts of micropore in catalytic reaction, because hole can be blocked in the big reagent access aperture of viscosity, causes the reduction of response speed.At present, there are many approach application to poromerics, for instance: in-situ synthesis, adsorption precipitation self-assembly method, emulsion template method.But, we select emulsion template method to remove poromerics, because droplet size reaches the High Internal Phase Emulsion of more than 74% provides a kind of simple method synthesizing large pore material, obtain this large pore material by monomer in polymeric continuous phase and can overcome the restriction of reagent, and the aperture of this macropore can be changed by the ratio of adjustment oil phase and aqueous phase.Traditionally with poisonous surfactant stable emulsion, it is seen then that stablizing of emulsion is that a challenge is applied in synthesizing porous polymer aspect.Interface there is very high-octane granule carry out stable pik woods High Internal Phase Emulsion more more stable than traditional High Internal Phase Emulsion.Pik woods High Internal Phase Emulsion polymerization obtain be autonomous closure hole between not have connection polymer, with the pik Lin Gaonei phase-polymerization of stable particle and surfactant jointly stabilizing obtain be between hole connect polymer.At present, the few's High Internal Phase Emulsion and pik woods High Internal Phase Emulsion method remove synthesizing porous polymer solids acid catalyst.
Summary of the invention
The present invention obtains silicon dioxide granule by hydrolytic condensation, and use γ-methacryloxypropyl trimethoxy silane to be modified strengthening its hydrophobicity to it, then Span 80(span80 in varing proportions) and hydrophobic silicon ball particle be used as double, two emulsifying agent, it aqueous phase is deionized water, potassium peroxydisulfate, potassium sulfate and sodium p styrene sulfonate, oil phase is divinylbenzene (DVB) and 2, 2'-azodiisobutyronitrile (AIBN), form stable pik woods High Internal Phase Emulsion, radical polymerization obtains macroporous polymer, then the obtaining macropore and there is the solid acid catalyst of strong acid catalysis effect of sulfonation.And solid acid catalyst is applied to cellulose conversion, obtain 5 hydroxymethyl furfural.
The technical solution used in the present invention is:
A kind of method that macropore solid acid catalyst is prepared in pickering emulsion polymerization, carries out as steps described below:
(1) synthesis of silicon ball and silicon ball are hydrophobic modified
Tetraethyl orthosilicate (TEOS) is added CH3CH2OH and H2In the aqueous solution of O, add the NH of 22 ~ 25% mass ratioes subsequently inside3·H2O, stirs 1-1.5 hour with 600 ~ 800rpm/min at 30 DEG C, after centrifuge, dries 3 ~ 4 hours, obtain uniform silicon ball in 60 ~ 80 DEG C of vacuum drying ovens.The silicon ball of synthesis, toluene, water and γ-methacryloxypropyl trimethoxy silane (KH-570) mixing, stir 20 ~ 24 hours at 40 DEG C, after centrifuge, dry 3 ~ 4 hours in 60 ~ 80 DEG C of vacuum drying ovens, obtain hydrophobic silicon ball.
(2) synthesis of the pik woods High Internal Phase Emulsion polymer being polymerized and sulfonation
First, hydrophobic silicon ball, divinylbenzene (DVB), Span 80(span80) and azodiisobutyronitrile (AIBN) by a series of proportions as oil phase, then, potassium peroxydisulfate, potassium sulfate and sodium p styrene sulfonate (SSS) add in deionized water as aqueous phase, last under stirring with 900 ~ 1100rpm/min, aqueous phase is added dropwise in oil phase, after 10 ~ 20 minutes, is prepared into stable pik woods High Internal Phase Emulsion.It is carried out thermal-initiated polymerization reaction in 18 ~ 24 hours 60 ~ 65 DEG C of maintenances.Polymer acetone surname extraction 20 ~ 24 hours at 60 ~ 80 DEG C obtained, last pik woods high internal phase polymeric is at 25 ~ 30 DEG C of vacuum dryings.
(3) concentrated sulphuric acid of the pik woods high internal phase polymeric obtained and 98% mass ratio is reacted 10 ~ 12 hours at 60 ~ 70 DEG C, then filter, clean repeatedly with deionized water until sulphuric acid is cleaned, finally at the oven drying 3 ~ 4 hours of 60 ~ 80 DEG C, obtain the eurypyloue solid acid catalyst of tool.
Wherein the tetraethyl orthosilicate described in step (1), NH3·H2O、CH3CH2OH、H2O volume ratio is 5.8 ~ 6:3 ~ 3.14:85 ~ 90:9 ~ 11.
Wherein the silicon ball of the synthesis described in step (1), toluene, water and γ-methacryloxypropyl trimethoxy silane mixed proportion are 0.9 ~ 1:140 ~ 150:8 ~ 15:3.2 ~ 3.5(g/mL/mL/mL)
Wherein the content mixing ratio of each monomer of the hydrophobic silicon ball in the oil phase described in step (2), divinylbenzene, Span 80 and azodiisobutyronitrile has three groups, is 0.9 ~ 1:2.8 ~ 3:0:0.03 ~ 0.04 (g/mL/mL/g) respectively；0.2~0.3:2.8~3:0.17~0.2:0.03~0.04(g/mL/mL/g)；0.2~0.3:2.8~3:0.58~0.6:0.03~0.04(g/mL/mL/g)
Wherein the deionized water described in step (2), potassium peroxydisulfate, potassium sulfate and sodium p styrene sulfonate mass ratio are 16 ~ 16.8:0.03 ~ 0.04:0.07 ~ 0.08:0.18 ~ 0.2.
The technological merit of the present invention: the polymer P DVB-SSS-X-SO of the pik woods High Internal Phase Emulsion of a series of polymerizations3The H volume of Span 80 (X represent) has the loose structure of acidity, macropore；Wherein loose structure can be effectively increased specific surface area reach strengthen catalytic effect；Stable particle layer makes the polymer machinery intensity height of acquisition, and acid site is survivable；Aperture can reach adjustability by changing the volume ratio of oil phase and aqueous phase；PDVB-SSS-X-SO3H has certain hydrophobicity, can realize quickly separating from the mixture of reaction；PDVB-SSS-X-SO simultaneously3It is effective and reproducible that H has acidic catalyst, and catalysis fibre element changes into 5 hydroxymethyl furfural and obtains significantly high productivity.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of silicon ball (a) and hydrophobicity silicon ball (b) prepared in embodiment 1.As can be seen from the figure embodiment 1 obtains the average diameter of silicon ball and hydrophobicity silicon ball is 100 nanometers, finds out from b, and there is the shade of one layer of list on ball surface, illustrates that hydrophobic group has successfully connected, the hydrophobic modified success of silicon ball.
Fig. 2 is PDVB-SSS-0-HF-SO before the sulfonation prepared in embodiment 13H(a)、PDVB-SSS-0-HF-SO3H(b)、PDVB-SSS-0.2-SO3H (C) and PDVB-SSS-0.6-SO3The scanning electron microscope (SEM) photograph of H (d).Finding out from a, embodiment 1 obtains PDVB-SSS-0-HF-SO before sulfonation3The average pore size of H is 100 microns.Find out from b, the PDVB-SSS-0-HF-SO that embodiment 1 obtains3H average pore size is also 100 microns, illustrates that the structure of material is not affected and the fastness of pore structure by sulfonation.Find out from c, the PDVB-SSS-0.2-HF-SO that embodiment 1 obtains3H average pore size is 5 microns.Find out from b, the PDVB-SSS-0.6-HF-SO that embodiment 1 obtains3H average pore size is 20 microns
Fig. 3 is PDVB-SSS-0-HF-SO in embodiment 13H (A) and PDVB-SSS-0.2-SO3Fourier-the infrared spectrogram (b) of H (B).In infrared spectrogram, 1039cm-1Corresponding is the peak of C S, 1170cm-1It is SO3The absworption peak of H.As can be seen from the figure the polymer P DVB-SSS-X-SO of embodiment 13H sulfonation success.
Fig. 4 is PDVB-SSS-0-HF-SO in embodiment 13H (a) and PDVB-SSS-0.6-SO3The x-ray photoelectron power spectrum of H (b).It can be seen that embodiment 1 obtains polymer P DVB-SSS-0-HF-SO from figure A3H and PDVB-SSS-0.6-HF-SO3H contains C, O, S element, and 284.7 and the 275.4eV that scheme the C1s in B correspond to C-C and C-S respectively, and they all show that sulfonic acid group successfully connects.In figure C, the combination of S2p can be not changed in, and illustrates after cleaning silicon ball with HF, the sulfonation of polymer not to be affected.
Fig. 5 is PDVB-SSS-0-SO in embodiment 13H(a),PDVB-SSS-0-HF-SO3H(b),PDVB-SSS-0.2-SO3H (c) and PDVB-SSS-0.6-SO3The ammonia temperature programmed desorption figure of H (d).As can be seen from the figure polymer P DVB-SSS-X-HF-SO3H shows the strong kind of two or more acid.Embodiment 1 obtains PDVB-SSS-0-SO3H、PDVB-SSS-0-HF-SO3H、PDVB-SSS-0.2-SO3H and PDVB-SSS-0.6-SO3The sour total amount of H is 170,207,233 and 244 μm of ol/g respectively.
Fig. 6 uses PDVB-SSS-0.2-SO in embodiment 13H is used as catalyst and changes into the reaction condition figure of 5 hydroxymethyl furfural to optimize glucose.PDVB-SSS-0.2-SO3H makes consumption (A) and time and temperature (B) impact on 5 hydroxymethyl furfural respectively when 40mg catalyst and 2g ionic liquid.It can be seen that the reaction condition of optimum is: 40mg catalyst, 2g ionic liquid, reaction temperature are 120 DEG C and the response time is 2 hours.
Detailed description of the invention
A kind of pickering emulsion polymerization described in technique scheme prepare macropore solid acid catalyst method implement analyze particularly as follows:
Pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the catalyst adding 40mg in reaction vessel, reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, the computational methods of the conversion ratio of 5 hydroxymethyl furfural be as follows:
Wherein n1(mol) it is the material amount analyzing the 5 hydroxymethyl furfural obtained, n0(mol) the total material amount of unit contained by cellulose,
Below in conjunction with being embodied as example, the present invention will be further described.
Embodiment 1:
A kind of method that macropore solid acid catalyst is prepared in pickering emulsion polymerization, it is characterised in that carry out as steps described below:
(1) synthesis of silicon ball and silicon ball are hydrophobic modified
5.8mL tetraethyl orthosilicate (TEOS) is added 85mLCH3CH2OH and 9mLH2In the aqueous solution of O, add 3mLNH subsequently inside3·H2O, at 30 DEG C, 800rpm/min stirs 1 hour, after centrifugal, dry 3 hours, obtain uniform silicon ball in 80 DEG C of vacuum drying ovens.The 0.9g silicon ball of synthesis, 140mL toluene, 8mL water and 3.2mL γ-methacryloxypropyl trimethoxy silane mixing, at 40 DEG C, 800rpm/min stirs 24 hours, after centrifuge, dry 3 hours in 80 DEG C of vacuum drying ovens, obtain hydrophobic silicon ball.
(2) synthesis of the pik woods High Internal Phase Emulsion polymer being polymerized and sulfonation
First, the hydrophobic silicon ball of 0.9g, 2.8mL divinylbenzene (DVB) and 0.03g azodiisobutyronitrile (AIBN)；The hydrophobic silicon ball of 0.2g, 2.8mL divinylbenzene (DVB), 0.17g Span 80(span80) and 0.03g azodiisobutyronitrile (AIBN)；The hydrophobic silicon ball of 0.2g, 2.8mL divinylbenzene (DVB), 0.58g Span 80(span80) and 0.03g azodiisobutyronitrile (AIBN) three series prepare respectively as oil phase, then, 0.03g potassium peroxydisulfate, 0.07g potassium sulfate and 0.18g sodium p styrene sulfonate (SSS) add in 16g deionized water as aqueous phase, under high velocity agitation finally, aqueous phase is added dropwise in oil phase, after 10-20 minute, it is prepared into respectively stable pik woods High Internal Phase Emulsion.It is carried out thermal-initiated polymerization reaction in 18-24 hour 60-65 DEG C of maintenance.The polymer acetone obtained respectively surname extraction 24 hours at 80 DEG C, last pik woods high internal phase polymeric is at 30 DEG C of vacuum dryings.
Respectively the concentrated sulphuric acid of the pik woods high internal phase polymeric obtained and 98% is reacted 12 hours at 70 DEG C, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, the last oven drying at 80 DEG C 3 hours, obtains their called after PDVB-SSS-X-SO of acidic polymer solid acid with porous3The H volume of span80 (X represent) and PDVB-SSS-X-HF-SO3H uses hydrofluoric acid clean before representing sulfonation.
2, catalytic performance analysis test
(1) pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the productivity according to result calculating 5 hydroxymethyl furfural.
Pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0-HF-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the product according to result calculating 5 hydroxymethyl furfural.
Result shows: PDVB-SSS-0-SO3The productivity 18.9% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0-HF-SO3The productivity 20.6% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0-HF-SO3H catalytic effect is apparently higher than PDVB-SSS-0-SO3H。
(2) pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0.2-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the productivity according to result calculating 5 hydroxymethyl furfural.
Pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0.6-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the product according to result calculating 5 hydroxymethyl furfural.
Result shows: PDVB-SSS-0.2-SO3The productivity 29.6% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0.6-SO3The productivity 15.5% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0.2-SO3H catalytic effect is apparently higher than PDVB-SSS-0.6-SO3H。
3, the physicochemical property of material characterizes
(1) preparing, according to the method for embodiment 1, the emulsion that multiclass oil phase, oil mixing with water phase and high-speed stirred process respectively, result shows that the method can prepare stable pik woods High Internal Phase Emulsion.
(2) transmission electron microscope picture of silicon ball and hydrophobicity silicon ball in embodiment 1 is tested.It is 100 nanometers that Fig. 1 result shows that embodiment 1 obtains the average diameter of silicon ball and hydrophobicity silicon ball.In the transmission electron microscope picture of hydrophobicity silicon ball, there is the shade of one layer of list on ball surface, illustrates that hydrophobic group has successfully connected, the hydrophobic modified success of silicon ball.
(3) PDVB-SSS-0-HF-SO before sulfonation is tested in embodiment 13H、PDVB-SSS-0-HF-SO3H、PDVB-SSS-0.2-SO3H and PDVB-SSS-0.6-SO3The scanning electron microscope (SEM) photograph of H.From figure 2 it can be seen that from PDVB-SSS-0-HF-SO before sulfonation3Finding out in H scanning electron microscope, embodiment 1 obtains PDVB-SSS-0-HF-SO before sulfonation3The average pore size of H is 100 microns.From PDVB-SSS-0-HF-SO3H scanning electron microscope is found out, the PDVB-SSS-0-HF-SO that embodiment 1 obtains3H average pore size is also 100 microns, illustrates that the structure of material is not affected and the fastness of pore structure by sulfonation.From PDVB-SSS-0.2-SO3H scanning electron microscope is found out, the PDVB-SSS-0.2-HF-SO that embodiment 1 obtains3H average pore size is 5 microns.From PDVB-SSS-0.6-SO3The scanning electron microscope (SEM) photograph of H is found out, the PDVB-SSS-0.6-HF-SO that embodiment 1 obtains3H average pore size is 20 microns
(4) PDVB-SSS-0-HF-SO in embodiment 1 is tested3H and PDVB-SSS-0.2-SO3Fourier-the infrared spectrogram of H.In the infrared spectrogram of Fig. 3,1039cm-1Corresponding is the peak of C S, 1170cm-1It is SO3The absworption peak of H.As can be seen from the figure the polymer P DVB-SSS-X-SO of embodiment 13H sulfonation success.
(5) PDVB-SSS-0-HF-SO in embodiment 1 is tested3H and PDVB-SSS-0.6-SO3The x-ray photoelectron power spectrum of H.Figure 4, it is seen that embodiment 1 obtains polymer P DVB-SSS-0-HF-SO3H and PDVB-SSS-0.6-HF-SO3H contains C, O, S element, and the 284.7 of C1s and 275.4eV correspond to C-C and C-S respectively, it was shown that sulfonic acid group successfully connects.The combination of S2p simultaneously can be not changed in, and illustrates after cleaning silicon ball with HF, the sulfonation of polymer not to be affected.
(6) PDVB-SSS-0-SO in embodiment 1 is tested3H,PDVB-SSS-0-HF-SO3H,PDVB-SSS-0.2-SO3H and PDVB-SSS-0.6-SO3The ammonia temperature programmed desorption figure of H.As can be seen from Figure 5 polymer P DVB-SSS-X-HF-SO3H shows the strong kind of two or more acid.Embodiment 1 obtains PDVB-SSS-0-SO3H、PDVB-SSS-0-HF-SO3H、PDVB-SSS-0.2-SO3H and PDVB-SSS-0.6-SO3The sour total amount of H is 170,207,233 and 244 μm of ol/g respectively.
(7) testing in embodiment 1, Fig. 6 represents and uses PDVB-SSS-0.2-SO3H is used as catalyst and changes into the reaction condition figure of 5 hydroxymethyl furfural to optimize glucose.By inquiring into PDVB-SSS-0.2-SO3H makes consumption and time and the temperature impact on 5 hydroxymethyl furfural respectively when 40mg catalyst and 2g ionic liquid.It can be seen that the reaction condition of optimum is in A, B figure from Fig. 6: 40mg catalyst, 2g ionic liquid, reaction temperature are 120 DEG C and the response time is 2 hours.
Embodiment 2:
A kind of method that macropore solid acid catalyst is prepared in pickering emulsion polymerization, it is characterised in that carry out as steps described below:
(1) synthesis of silicon ball and silicon ball are hydrophobic modified
6mL tetraethyl orthosilicate (TEOS) is added 90mLCH3CH2OH and 10mLH2In the aqueous solution of O, add 3.14mLNH subsequently inside3·H2O, at 30 DEG C, 600rpm/min stirs 1.5 hours, after centrifugal, dry 4 hours, obtain uniform silicon ball in 60 DEG C of vacuum drying ovens.The 1g silicon ball of synthesis, 150mL toluene, 15mL water and 3.5mL γ-methacryloxypropyl trimethoxy silane mixing, at 40 DEG C, 600rpm/min stirs 20 hours, after centrifuge, dry 4 hours in 60 DEG C of vacuum drying ovens, obtain hydrophobic silicon ball.
(2) synthesis of the pik woods High Internal Phase Emulsion polymer being polymerized and sulfonation
First, the hydrophobic silicon ball of 1g, 3mL divinylbenzene (DVB) and 0.04g azodiisobutyronitrile (AIBN)；The hydrophobic silicon ball of 0.3g, 3mL divinylbenzene (DVB), 0.2g Span 80(span80) and 0.04g azodiisobutyronitrile (AIBN)；The hydrophobic silicon ball of 0.3g, 3mL divinylbenzene (DVB), 0.6g Span 80(span80) and 0.04g azodiisobutyronitrile (AIBN) three series prepare respectively as oil phase, then, 0.04g potassium peroxydisulfate, 0.08g potassium sulfate and 0.2g sodium p styrene sulfonate (SSS) add in 16.8g deionized water as aqueous phase, under high velocity agitation finally, aqueous phase is added dropwise in oil phase, after 10-20 minute, it is prepared into respectively stable pik woods High Internal Phase Emulsion.It is carried out thermal-initiated polymerization reaction in 18-24 hour 60-65 DEG C of maintenance.The polymer acetone obtained respectively surname extraction 24 hours at 80 DEG C, last pik woods high internal phase polymeric is at 30 DEG C of vacuum dryings.
Respectively the concentrated sulphuric acid of the pik woods high internal phase polymeric obtained and 98% mass ratio is reacted 10 hours at 60 DEG C, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, the last oven drying at 60 DEG C 4 hours, obtains their called after PDVB-SSS-X-SO of acidic polymer solid acid with porous3The H volume of Span 80 (X represent) and PDVB-SSS-X-HF-SO3H uses hydrofluoric acid clean before representing sulfonation.
2, catalytic performance analysis test
(1) pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the productivity according to result calculating 5 hydroxymethyl furfural.
Pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0-HF-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the product according to result calculating 5 hydroxymethyl furfural.
Result shows: PDVB-SSS-0-SO3The productivity 18.9% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0-HF-SO3The productivity 20.6% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0-HF-SO3H catalytic effect is apparently higher than PDVB-SSS-0-SO3H。
(2) pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0.17-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the productivity according to result calculating 5 hydroxymethyl furfural.
Pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0.58-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the product according to result calculating 5 hydroxymethyl furfural.
Result shows: PDVB-SSS-0.17-SO3The productivity 29.6% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0.58-SO3The productivity 15.5% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0.17-SO3H catalytic effect is apparently higher than PDVB-SSS-0.58-SO3H。
Embodiment 3:
(1) synthesis of silicon ball and silicon ball are hydrophobic modified
5.9mL tetraethyl orthosilicate (TEOS) is added 87mLCH3CH2OH and 11mLH2In the aqueous solution of O, add 3.12mLNH subsequently inside3·H2O, at 30 DEG C, 700rpm/min stirs 1.2 hours, after centrifugal, dry 3.5 hours, obtain uniform silicon ball in 70 DEG C of vacuum drying ovens.The 0.95g silicon ball of synthesis, 145mL toluene, 12mL water and 3.4mL γ-methacryloxypropyl trimethoxy silane mixing, at 40 DEG C, 700rpm/min stirs 22 hours, after centrifuge, dry 3.5 hours in 80 DEG C of vacuum drying ovens, obtain hydrophobic silicon ball.
(2) synthesis of the pik woods High Internal Phase Emulsion polymer being polymerized and sulfonation
First, the hydrophobic silicon ball of 0.95g, 2.9mL divinylbenzene (DVB) and 0.035g azodiisobutyronitrile (AIBN)；The hydrophobic silicon ball of 0.29g, 2.9mL divinylbenzene (DVB), 0.18g Span 80(span80) and 0.035g azodiisobutyronitrile (AIBN)；The hydrophobic silicon ball of 0.29g, 2.9mL divinylbenzene (DVB), 0.59g Span 80(span80) and 0.035g azodiisobutyronitrile (AIBN) three series prepare respectively as oil phase, then, 0.035g potassium peroxydisulfate, 0.075g potassium sulfate and 0.19g sodium p styrene sulfonate (SSS) add in 16.5g deionized water as aqueous phase, under high velocity agitation finally, aqueous phase is added dropwise in oil phase, after 10-20 minute, it is prepared into respectively stable pik woods High Internal Phase Emulsion.It is carried out thermal-initiated polymerization reaction in 18-24 hour 60-65 DEG C of maintenance.The polymer acetone obtained respectively surname extraction 23 hours at 70 DEG C, last pik woods high internal phase polymeric is at 30 DEG C of vacuum dryings.
Respectively the concentrated sulphuric acid of the pik woods high internal phase polymeric obtained and 98% mass ratio is reacted 12 hours at 70 DEG C, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, the last oven drying at 80 DEG C 3 hours, obtains their called after PDVB-SSS-X-SO of acidic polymer solid acid with porous3The H volume of Span 80 (X represent) and PDVB-SSS-X-HF-SO3H uses hydrofluoric acid clean before representing sulfonation.
2, catalytic performance analysis test
(1) pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the productivity according to result calculating 5 hydroxymethyl furfural.
Pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0-HF-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the product according to result calculating 5 hydroxymethyl furfural.
Result shows: PDVB-SSS-0-SO3The productivity 18.9% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0-HF-SO3The productivity 20.6% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0-HF-SO3H catalytic effect is apparently higher than PDVB-SSS-0-SO3H。
(2) pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0.19-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the productivity according to result calculating 5 hydroxymethyl furfural.
Pretreatment 30 minutes at 0.1g cellulose and present 120 DEG C of 2g1-ethyl-3-methylimidazole chloride salt ions liquid, then at the PDVB-SSS-0.59-SO adding 40mg in reaction vessel3H, is reacting 2 hours.Add in reactor with a small amount of deionized water, then with brown volumetric flask constant volume, with the content of the 5 hydroxymethyl furfural that efficient liquid phase instrument analysis synthesizes, and the product according to result calculating 5 hydroxymethyl furfural.
Result shows: PDVB-SSS-0.19-SO3The productivity 29.6% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0.59-SO3The productivity 15.5% of the 5 hydroxymethyl furfural that H catalysis fibre element obtains, PDVB-SSS-0.19-SO3H catalytic effect is apparently higher than PDVB-SSS-0.59-SO3H。
Claims (3)
1. the method that macropore solid acid catalyst is prepared in a pickering emulsion polymerization, it is characterised in that carry out as steps described below:
(1) synthesis of silicon ball and silicon ball are hydrophobic modified
Tetraethyl orthosilicate (TEOS) is added CH3CH2OH and H2In the aqueous solution of O, adding mass percent concentration subsequently inside is 22 ~ 25%NH3·H2O, stirs 1-1.5 hour with 600 ~ 800rpm/min at 30 DEG C, after centrifuge, dries 3 ~ 4 hours, obtain uniform silicon ball in 60 ~ 80 DEG C of vacuum drying ovens；Wherein said tetraethyl orthosilicate (TEOS), NH3·H2O、CH3CH2OH、H2O volume ratio is 5.8 ~ 6:3 ~ 3.14:85 ~ 90:9 ~ 11；
The silicon ball of synthesis, toluene, water and γ-methacryloxypropyl trimethoxy silane (KH-570) mixing, stir 20 ~ 24 hours at 40 DEG C, after centrifuge, dry 3 ~ 4 hours in 60 ~ 80 DEG C of vacuum drying ovens, obtain hydrophobic silicon ball；The silicon ball of wherein said synthesis, toluene, water and γ-methacryloxypropyl trimethoxy silane (KH-570) mixed proportion are 0.9g ~ 1g:140mL ~ 150mL:8mL ~ 15mL:3.2mL ~ 3.5mL；
(2) synthesis of the pik woods High Internal Phase Emulsion polymer being polymerized and sulfonation
First, hydrophobic silicon ball, divinylbenzene (DVB), Span 80(span80) and azodiisobutyronitrile (AIBN) by a series of proportions as oil phase, then, potassium peroxydisulfate, potassium sulfate and sodium p styrene sulfonate (SSS) add in deionized water as aqueous phase, last under stirring with 900 ~ 1100rpm/min, aqueous phase is added dropwise in oil phase, after 10 ~ 20 minutes, is prepared into stable pik woods High Internal Phase Emulsion；It is carried out thermal-initiated polymerization reaction in 18 ~ 24 hours 60 ~ 65 DEG C of maintenances；Polymer acetone surname extraction 20 ~ 24 hours at 60 ~ 80 DEG C obtained, last pik woods high internal phase polymeric is at 25 ~ 30 DEG C of vacuum dryings；
(3) the pik woods high internal phase polymeric obtained and the concentrated sulphuric acid that mass percent concentration is 98% are reacted 10 ~ 12 hours at 60 ~ 70 DEG C, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, the last oven drying at 60 ~ 80 DEG C 3 ~ 4 hours, obtains the eurypyloue solid acid catalyst of tool.
2. the method that macropore solid acid catalyst is prepared in a kind of pickering emulsion polymerization according to claim 1, it is characterized in that the content mixing ratio of each monomer of the hydrophobic silicon ball in the wherein oil phase described in step (2), divinylbenzene, Span 80 and azodiisobutyronitrile has three groups, be 0.9g ~ 1g:2.8mL ~ 3mL:0mL:0.03g ~ 0.04g respectively；0.2g~0.3g:2.8mL~3mL:0.17mL~0.2mL:0.03g~0.04g；0.2g~0.3g:2.8mL~3mL:0.58mL~0.6mL:0.03g~0.04g.
3. the method that macropore solid acid catalyst is prepared in a kind of pickering emulsion polymerization according to claim 1, it is characterised in that wherein the deionized water described in step (2), potassium peroxydisulfate, potassium sulfate and sodium p styrene sulfonate mass ratio are 16 ~ 16.8:0.03 ~ 0.04:0.07 ~ 0.08:0.18 ~ 0.2.
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