CN103992425A - Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization - Google Patents
Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization Download PDFInfo
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Abstract
The invention relates to a method for preparing a macroporous solid acid catalyst by Pickering emulsion polymerization, belonging to the technical field of preparation of environmental-function materials. The method comprises the following steps: carrying out hydrolytic condensation to synthesize silicon dioxide particles, modifying the silicon dioxide particles with gamma-methylacryloyloxypropyltrimethoxy silane to modify and enhance the hydrophobicity, and synthesizing a series of macroporous acidic functional polymerized Pickering high-inner-phase emulsion materials by using Span 80 and hydrophobic silicon ball granules in different ratios as a dual-emulsifier. The analysis on properties of the material by a scanning electron microscope, Fourier-infrared chromatograph, ammonia gas programmed heating desorption and X-ray photoelectron spectrum indicates that a medium-to-good yield is obtained when the cellulose is converted into 5-hydroxymethylfurfural by using a 1-ethyl-3-methylimidazolyl chlorine salt ionic liquid as the solvent under ordinary pressure. The research on the catalytic activity of the material indicates that the activity is not greatly lost after the material is circulated at least four times.
Description
Technical field
The present invention relates to a kind of pickering emulsion polymerization and prepare the method for macropore solid acid catalyst, belong to environment functional material preparing technical field.
Background technology
Along with the minimizing of fossil oil deposit, people extremely pay close attention to abundant reproducible cellulose resource and remove to replace fossil oil.Produce at Mierocrystalline cellulose in the use of fuel, the synthetic 5 hydroxymethyl furfural of single stage method is a very important step.5 hydroxymethyl furfural can very easily change into the biofuel of the furans of energy substitute fossil fuels and chemical by condensation and hydrogenation reduction.For example, 5 hydroxymethyl furfural can hydrogenating reduction generates 2,5-dimethyl furan, and it is a kind of than also high potentiality fuel of ethanol energy density.Can from 5 hydroxymethyl furfural obtain 2,5-diformyl furans and 2,5-dihydroxymethyl furans are widely used aspect synthetic polymer.
In recent years, people are used as catalyzer with various acid and remove to study cellulose conversion 5 hydroxymethyl furfural.Use the homogeneous acid catalyst as hydrochloric acid and organic acid to go catalyzed degradation Mierocrystalline cellulose can obtain the 5 hydroxymethyl furfural that productive rate is very high, but under such condition, have a lot of shortcomings, as easy etching apparatus, by product is many, it is difficult to separate, and contaminate environment, to the toxicity of human body.Along with the enhancing of environmental protection consciousness, people accelerate to use heterogeneous an acidic catalyst especially solid acid go degraded cellulose to obtain 5 hydroxymethyl furfural because their environmental protection, better circulation, easily separate, corrosive equipment not.Solid acid catalyst is widely used in various acid catalyzed reactions, in the solid catalyst of the fixing liquid acid of solid, zeolite, sulfide, natural clay mineral, ion exchange resin, heteropolyacid, oxide compound, solid super-strong acid, metal-salt, sulfonation carbon-based solid acid and these types of polymer-based carbon solid acid, the polymer-based carbon solid acid catalyst application of the little and outstanding catalytic effect of density is very active.Along with going deep into of people understanding, the acidic resins that it is found that perfluorinated sulfonic acid type provide correct direction for the solid acid of the hydrophobic network structure of synthetic heat-flash stability, still, and the few and little application having affected as effective acid catalyzer of specific surface area in hole.
Because porous catalyst specific surface area is large, reaction conditions is gentle, excellent catalytic effect, environmental friendliness, circulating effect are good, separate and easily and not corrode these advantages of instrument, allow them be widely used in field of catalytic reactions.But the porous catalyst that has a large amount of micropores in catalyzed reaction has certain restriction to reagent, because the large reagent of viscosity enters Kong Zhonghui, hole is blocked, cause the reduction of speed of response.At present, there are many methods to apply to poromerics, for example: in-situ synthesis, adsorption precipitation self-assembly method, emulsion template method.But, we select emulsion template method to remove poromerics, because reaching more than 74% High Internal Phase Emulsion, droplet size provides a kind of simple method of synthetic large pore material, obtained this large pore material and can overcome the restriction of reagent by monomer in polymerization external phase, and the aperture of this macropore can be changed by the ratio that regulates oil phase and water.Use traditionally poisonous tensio-active agent stable emulsion, visible, the stable of emulsion is that a challenge is applied in synthesizing porous polymkeric substance aspect.On interface, there is very high-octane particle to carry out stable pik woods High Internal Phase Emulsion more stable than traditional High Internal Phase Emulsion.What the polymerization of pik woods High Internal Phase Emulsion obtained is the polymkeric substance that there is no connection between independent blind hole, and what obtain by the pik Lin Gaonei phase-polymerization of stable particle and tensio-active agent jointly stabilizing is the polymkeric substance being communicated with between hole.At present, the few remove synthesizing porous polymer solids acid catalyst by High Internal Phase Emulsion and pik woods High Internal Phase Emulsion method.
Summary of the invention
The present invention has obtained silicon dioxide granule by hydrolytic condensation, and use γ-methacryloxypropyl trimethoxy silane to carry out modification to it to strengthen its hydrophobicity, the then 80(span80 of class of department in varing proportions) and hydrophobic silicon ball particle be used as pair emulsifying agents, it in water, is deionized water, Potassium Persulphate, potassium sulfate and sodium p styrene sulfonate, oil phase is Vinylstyrene (DVB) and 2, 2'-Diisopropyl azodicarboxylate (AIBN), form stable pik woods High Internal Phase Emulsion, radical polymerization obtains macroporous polymer, then having obtained 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 method for macropore solid acid catalyst is prepared in pickering emulsion polymerization, carries out according to following step:
(1) the synthetic and silicon ball of silicon ball is hydrophobic modified
Tetraethoxy (TEOS) is added to CH
3cH
2oH and H
2in the aqueous solution of O, add inside subsequently the NH of 22 ~ 25% mass ratioes
3h
2o stirs 1-1.5 hour with 600 ~ 800rpm/min at 30 DEG C, centrifugal by whizzer after, in 60 ~ 80 DEG C of vacuum drying ovens dry 3 ~ 4 hours, obtained uniform silicon ball.Synthetic silicon ball, toluene, water and γ-methacryloxypropyl trimethoxy silane (KH-570) are mixed, at 40 DEG C, stir 20 ~ 24 hours, after centrifugal by whizzer, in 60 ~ 80 DEG C of vacuum drying ovens, be dried 3 ~ 4 hours, obtained hydrophobic silicon ball.
(2) the synthetic and sulfonation of the pik woods High Internal Phase Emulsion polymkeric substance of polymerization
First, hydrophobic silicon ball, Vinylstyrene (DVB), the 80(span80 of class of department) and Diisopropyl azodicarboxylate (AIBN) prepare as oil phase in a series of ratios, then, Potassium Persulphate, potassium sulfate and sodium p styrene sulfonate (SSS) add in deionized water as water, finally under stirring with 900 ~ 1100rpm/min, water dropwise adds in oil phase, after 10 ~ 20 minutes, is prepared into stable pik woods High Internal Phase Emulsion.It is kept carrying out for 18 ~ 24 hours thermal-initiated polymerization reaction at 60 ~ 65 DEG C.The polymkeric substance obtaining extracts 20 ~ 24 hours by acetone Soxhlet at 60 ~ 80 DEG C, and last pik woods high internal phase polymeric is 25 ~ 30 DEG C of vacuum-dryings.
(3) vitriol oil of the pik woods high internal phase polymeric obtaining and 98% mass ratio is reacted 10 ~ 12 hours at 60 ~ 70 DEG C, then filter, repeatedly until sulfuric acid is cleaned, finally, the oven drying of 60 ~ 80 DEG C 3 ~ 4 hours, obtain the eurypyloue solid acid catalyst of tool by washed with de-ionized water.
Wherein tetraethoxy, the NH described in step (1)
3h
2o, CH
3cH
2oH, H
2o volume ratio is 5.8 ~ 6: 3 ~ 3.14: 85 ~ 90: 9 ~ 11.
Wherein the synthetic silicon ball described in step (1), toluene, water and γ-methacryloxypropyl trimethoxy silane blending ratio are 0.9 ~ 1: 140 ~ 150: 8 ~ 15: 3.2 ~ 3.5(g/mL/mL/mL)
Wherein the content ratio of mixture of each monomer of hydrophobic silicon ball, Vinylstyrene, class of department 80 and the Diisopropyl azodicarboxylate in the oil phase described in step (2) has three groups, is respectively 0.9 ~ 1: 2.8 ~ 3: 0: 0.03 ~ 0.04 (g/mL/mL/g); 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 Persulphate, 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.
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 polymerizations
3h (X represents the volume of Si Ban 80) has the vesicular structure of acidity, macropore; Wherein vesicular structure can effectively increase specific surface area and reaches enhancing catalytic effect; Stable particle layer makes the polymer machinery intensity of acquisition high, and acid site is survivable; Aperture can reach adjustability by the volume ratio that changes oil phase and water; PDVB-SSS-X-SO
3h has certain hydrophobicity, can realize the mixture separation from reaction fast; PDVB-SSS-X-SO simultaneously
3it is effective and reproducible that H has acidic catalyst, and catalyse cellulose changes into 5 hydroxymethyl furfural and obtains very high productive rate.
Brief description of the drawings
Fig. 1 is the silicon ball (a) of preparation in embodiment 1 and the transmission electron microscope picture of hydrophobicity silicon ball (b).As can be seen from the figure to obtain the mean diameter of silicon ball and hydrophobicity silicon ball be 100 nanometers to embodiment 1, from b, finds out, there is the shade of one deck list on ball surface, illustrates that hydrophobic grouping has successfully connected, the hydrophobic modified success of silicon ball.
Fig. 2 is the front PDVB-SSS-0-HF-SO of the sulfonation of preparation in embodiment 1
3h (a), PDVB-SSS-0-HF-SO
3h (b), PDVB-SSS-0.2-SO
3h (C) and PDVB-SSS-0.6-SO
3the scanning electron microscope (SEM) photograph of H (d).From a, find out, embodiment 1 obtains the front PDVB-SSS-0-HF-SO of sulfonation
3the mean pore size of H is 100 microns.From b, find out the PDVB-SSS-0-HF-SO that embodiment 1 obtains
3h mean pore size is also 100 microns, illustrates that sulfonation does not affect and the stability of pore structure the structure of material.From c, find out the PDVB-SSS-0.2-HF-SO that embodiment 1 obtains
3h mean pore size is 5 microns.From b, find out the PDVB-SSS-0.6-HF-SO that embodiment 1 obtains
3h mean pore size is 20 microns
Fig. 3 is PDVB-SSS-0-HF-SO in embodiment 1
3h (A) and PDVB-SSS-0.2-SO
3fourier-infrared spectrogram (b) of H (B).In infrared spectrogram, 1039 cm
-1corresponding is the peak of C – S, 1170cm
-1shi – SO
3the absorption peak of H.As can be seen from the figure polymer P DVB-SSS-X-SO of embodiment 1
3h sulfonation success.
Fig. 4 is PDVB-SSS-0-HF-SO in embodiment 1
3h (a) and PDVB-SSS-0.6-SO
3the x-ray photoelectron power spectrum of H (b).From figure A, can find out, embodiment 1 obtains polymer P DVB-SSS-0-HF-SO
3h and PDVB-SSS-0.6-HF-SO
3h contains C, O, S element, and 284.7 and 275.4 eV of the C1s of figure in B corresponding C-C and C-S respectively, and they all show that sulfonic acid group successfully connects.In figure C, the combination of S2p can not change, and illustrates with after HF cleaning silicon ball, the sulfonation of polymkeric substance not being affected.
Fig. 5 is PDVB-SSS-0-SO in embodiment 1
3h (a), PDVB-SSS-0-HF-SO
3h (b), PDVB-SSS-0.2-SO
3h (c) and PDVB-SSS-0.6-SO
3the ammonia temperature programmed desorption(TPD) figure of H (d).As can be seen from the figure polymer P DVB-SSS-X-HF-SO
3h shows the strong kind of two or more acid.Embodiment 1 obtains PDVB-SSS-0-SO
3h, PDVB-SSS-0-HF-SO
3h, PDVB-SSS-0.2-SO
3h and PDVB-SSS-0.6-SO
3the sour total amount of H is respectively 170,207,233 and 244 μ mol/g.
Fig. 6 uses PDVB-SSS-0.2-SO in embodiment 1
3h is used as catalyzer and optimizes conversion of glucose and become the reaction conditions figure of 5 hydroxymethyl furfural.PDVB-SSS-0.2-SO
3the usage quantity (A) of H and time and temperature (B) impact on 5 hydroxymethyl furfural respectively under 40 mg catalyzer and 2g ionic liquid condition.As we know from the figure, optimum reaction conditions is: 40 mg catalyzer, 2g ionic liquid, temperature of reaction are that 120 DEG C and reaction times are 2 hours.
Embodiment
The method enforcement analysis that macropore solid acid catalyst is prepared in a kind of pickering emulsion polymerization described in technique scheme is specially:
Pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the catalyzer that adds 40mg in reaction vessel, reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, the method for calculation of the transformation efficiency of 5 hydroxymethyl furfural are as follows:
Wherein
n 1 (mol)the amount of analyzing the 5 hydroxymethyl furfural obtaining,
n 0 (mol) be the total amount in the contained unit of Mierocrystalline cellulose,
Below in conjunction with concrete embodiment, the present invention will be further described.
Embodiment 1:
A method for macropore solid acid catalyst is prepared in pickering emulsion polymerization, it is characterized in that carrying out according to following step:
(1) the synthetic and silicon ball of silicon ball is hydrophobic modified
5.8 mL tetraethoxys (TEOS) are added to 85mLCH
3cH
2oH and 9mLH
2in the aqueous solution of O, add inside subsequently 3mLNH
3h
2o, at 30 DEG C, 800rpm/min stirs 1 hour, centrifugal after, in 80 DEG C of vacuum drying ovens dry 3 hours, obtained uniform silicon ball.Synthetic 0.9g silicon ball, 140mL toluene, 8mL water and 3.2mL γ-methacryloxypropyl trimethoxy silane is mixed, at 40 DEG C, 800rpm/min stirs 24 hours, after centrifugal with whizzer, in 80 DEG C of vacuum drying ovens, be dried 3 hours, obtained hydrophobic silicon ball.
(2) the synthetic and sulfonation of the pik woods High Internal Phase Emulsion polymkeric substance of polymerization
First, the hydrophobic silicon ball of 0.9g, 2.8mL Vinylstyrene (DVB) and 0.03g Diisopropyl azodicarboxylate (AIBN); The hydrophobic silicon ball of 0.2g, 2.8mL Vinylstyrene (DVB), the 80(span80 of class of 0.17g department) and 0.03g Diisopropyl azodicarboxylate (AIBN); The hydrophobic silicon ball of 0.2g, 2.8mL Vinylstyrene (DVB), the 80(span80 of class of 0.58g department) and 0.03g Diisopropyl azodicarboxylate (AIBN) three series prepare respectively as oil phase, then, 0.03g Potassium Persulphate, 0.07g potassium sulfate and 0.18g sodium p styrene sulfonate (SSS) add in 16g deionized water as water, finally under high-speed stirring, water dropwise adds in oil phase, after 10-20 minute, it is prepared into respectively to stable pik woods High Internal Phase Emulsion.It is kept carrying out for 18-24 hour thermal-initiated polymerization reaction at 60-65 DEG C.The polymkeric substance obtaining respectively extracts 24 hours by acetone Soxhlet at 80 DEG C, and last pik woods high internal phase polymeric is 30 DEG C of vacuum-dryings.
Respectively the vitriol oil of the pik woods high internal phase polymeric obtaining and 98% is reacted 12 hours at 70 DEG C, then filter, with washed with de-ionized water repeatedly until sulfuric acid clean, finally the oven drying of 80 DEG C 3 hours, obtain having their called after PDVB-SSS-X-SO of acidic polymer solid acid of porous
3h (X represents the volume of span80) and PDVB-SSS-X-HF-SO
3h represents to have used hydrofluoric acid clean before sulfonation.
2, catalytic performance analytical test
(1) pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the productive rate of 5 hydroxymethyl furfural according to result.
Pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0-HF-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the product of 5 hydroxymethyl furfural according to result.
Result shows: PDVB-SSS-0-SO
3the productive rate 18.9% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0-HF-SO
3the productive rate 20.6% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0-HF-SO
3h catalytic effect is apparently higher than PDVB-SSS-0-SO
3h.
(2) pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0.2-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the productive rate of 5 hydroxymethyl furfural according to result.
Pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0.6-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the product of 5 hydroxymethyl furfural according to result.
Result shows: PDVB-SSS-0.2-SO
3the productive rate 29.6% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0.6-SO
3the productive rate 15.5% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0.2-SO
3h catalytic effect is apparently higher than PDVB-SSS-0.6-SO
3h.
3, the physicochemical property of material characterizes
(1) prepare respectively the emulsion of multiclass oil phase, oil mixing with water phase and high-speed stirring processing according to the method for embodiment 1, result shows that the method can prepare stable pik woods High Internal Phase Emulsion.
(2) tested the transmission electron microscope picture of silicon ball and hydrophobicity silicon ball in embodiment 1.Fig. 1 result shows that the mean diameter that embodiment 1 obtains silicon ball and hydrophobicity silicon ball is 100 nanometers.In the transmission electron microscope picture of hydrophobicity silicon ball, there is the shade of one deck list on ball surface, illustrates that hydrophobic grouping has successfully connected, the hydrophobic modified success of silicon ball.
(3) tested the front PDVB-SSS-0-HF-SO of sulfonation in embodiment 1
3h, PDVB-SSS-0-HF-SO
3h, PDVB-SSS-0.2-SO
3h and PDVB-SSS-0.6-SO
3the scanning electron microscope (SEM) photograph of H.As can be seen from Figure 2, PDVB-SSS-0-HF-SO from sulfonation
3in H scanning electron microscope, find out, embodiment 1 obtains the front PDVB-SSS-0-HF-SO of sulfonation
3the mean pore size of H is 100 microns.From PDVB-SSS-0-HF-SO
3in H scanning electron microscope, find out the PDVB-SSS-0-HF-SO that embodiment 1 obtains
3h mean pore size is also 100 microns, illustrates that sulfonation does not affect and the stability of pore structure the structure of material.From PDVB-SSS-0.2-SO
3in H scanning electron microscope, find out the PDVB-SSS-0.2-HF-SO that embodiment 1 obtains
3h mean pore size is 5 microns.From PDVB-SSS-0.6-SO
3in the scanning electron microscope (SEM) photograph of H, find out the PDVB-SSS-0.6-HF-SO that embodiment 1 obtains
3h mean pore size is 20 microns
(4) tested PDVB-SSS-0-HF-SO in embodiment 1
3h and PDVB-SSS-0.2-SO
3fourier-infrared spectrogram of H.In the infrared spectrogram of Fig. 3,1039 cm
-1corresponding is the peak of C – S, 1170cm
-1shi – SO
3the absorption peak of H.As can be seen from the figure the polymer P DVB-SSS-X-SO of embodiment 1
3h sulfonation success.
(5) tested PDVB-SSS-0-HF-SO in embodiment 1
3h and PDVB-SSS-0.6-SO
3the x-ray photoelectron power spectrum of H.As can be seen from Figure 4, embodiment 1 obtains polymer P DVB-SSS-0-HF-SO
3h and PDVB-SSS-0.6-HF-SO
3h contains C, O, S element, and respectively corresponding C-C and C-S of 284.7 and 275.4 eV of C1s, shows that sulfonic acid group successfully connects.The combination of S2p simultaneously can not change, and illustrates with after HF cleaning silicon ball, the sulfonation of polymkeric substance not being affected.
(6) tested PDVB-SSS-0-SO in embodiment 1
3h, PDVB-SSS-0-HF-SO
3h, PDVB-SSS-0.2-SO
3h and PDVB-SSS-0.6-SO
3the ammonia temperature programmed desorption(TPD) figure of H.As can be seen from Figure 5 polymer P DVB-SSS-X-HF-SO
3h shows the strong kind of two or more acid.Embodiment 1 obtains PDVB-SSS-0-SO
3h, PDVB-SSS-0-HF-SO
3h, PDVB-SSS-0.2-SO
3h and PDVB-SSS-0.6-SO
3the sour total amount of H is respectively 170,207,233 and 244 μ mol/g.
(7) tested in embodiment 1, Fig. 6 represents to use PDVB-SSS-0.2-SO
3h is used as catalyzer and optimizes conversion of glucose and become the reaction conditions figure of 5 hydroxymethyl furfural.By inquiring into PDVB-SSS-0.2-SO
3the usage quantity of H and time and the temperature impact on 5 hydroxymethyl furfural respectively under 40 mg catalyzer and 2g ionic liquid condition.Known in A, B figure from Fig. 6, optimum reaction conditions is: 40 mg catalyzer, 2g ionic liquid, temperature of reaction are that 120 DEG C and reaction times are 2 hours.
Embodiment 2:
A method for macropore solid acid catalyst is prepared in pickering emulsion polymerization, it is characterized in that carrying out according to following step:
(1) the synthetic and silicon ball of silicon ball is hydrophobic modified
6 mL tetraethoxys (TEOS) are added to 90mLCH
3cH
2oH and 10mLH
2in the aqueous solution of O, add inside subsequently 3.14mLNH
3h
2o, at 30 DEG C, 600rpm/min stirs 1.5 hours, centrifugal after, in 60 DEG C of vacuum drying ovens dry 4 hours, obtained uniform silicon ball.Synthetic 1g silicon ball, 150mL toluene, 15mL water and 3.5mL γ-methacryloxypropyl trimethoxy silane is mixed, at 40 DEG C, 600rpm/min stirs 20 hours, after centrifugal with whizzer, in 60 DEG C of vacuum drying ovens, be dried 4 hours, obtained hydrophobic silicon ball.
(2) the synthetic and sulfonation of the pik woods High Internal Phase Emulsion polymkeric substance of polymerization
First, the hydrophobic silicon ball of 1g, 3mL Vinylstyrene (DVB) and 0.04g Diisopropyl azodicarboxylate (AIBN); The hydrophobic silicon ball of 0.3g, 3mL Vinylstyrene (DVB), the 80(span80 of class of 0.2g department) and 0.04g Diisopropyl azodicarboxylate (AIBN); The hydrophobic silicon ball of 0.3g, 3mL Vinylstyrene (DVB), the 80(span80 of class of 0.6g department) and 0.04g Diisopropyl azodicarboxylate (AIBN) three series prepare respectively as oil phase, then, 0.04g Potassium Persulphate, 0.08g potassium sulfate and 0.2g sodium p styrene sulfonate (SSS) add in 16.8 g deionized waters as water, finally under high-speed stirring, water dropwise adds in oil phase, after 10-20 minute, it is prepared into respectively to stable pik woods High Internal Phase Emulsion.It is kept carrying out for 18-24 hour thermal-initiated polymerization reaction at 60-65 DEG C.The polymkeric substance obtaining respectively extracts 24 hours by acetone Soxhlet at 80 DEG C, and last pik woods high internal phase polymeric is 30 DEG C of vacuum-dryings.
Respectively the vitriol oil of the pik woods high internal phase polymeric obtaining and 98% mass ratio is reacted 10 hours at 60 DEG C, then filter, with washed with de-ionized water repeatedly until sulfuric acid clean, finally the oven drying of 60 DEG C 4 hours, obtain having their called after PDVB-SSS-X-SO of acidic polymer solid acid of porous
3h (X represents the volume of Si Ban 80) and PDVB-SSS-X-HF-SO
3h represents to have used hydrofluoric acid clean before sulfonation.
2, catalytic performance analytical test
(1) pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the productive rate of 5 hydroxymethyl furfural according to result.
Pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0-HF-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the product of 5 hydroxymethyl furfural according to result.
Result shows: PDVB-SSS-0-SO
3the productive rate 18.9% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0-HF-SO
3the productive rate 20.6% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0-HF-SO
3h catalytic effect is apparently higher than PDVB-SSS-0-SO
3h.
(2) pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0.17-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the productive rate of 5 hydroxymethyl furfural according to result.
Pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0.58-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the product of 5 hydroxymethyl furfural according to result.
Result shows: PDVB-SSS-0.17-SO
3the productive rate 29.6% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0.58-SO
3the productive rate 15.5% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0.17-SO
3h catalytic effect is apparently higher than PDVB-SSS-0.58-SO
3h.
Embodiment 3:
(1) the synthetic and silicon ball of silicon ball is hydrophobic modified
5.9 mL tetraethoxys (TEOS) are added to 87mLCH
3cH
2oH and 11mLH
2in the aqueous solution of O, add inside subsequently 3.12mLNH
3h
2o, at 30 DEG C, 700rpm/min stirs 1.2 hours, centrifugal after, in 70 DEG C of vacuum drying ovens dry 3.5 hours, obtained uniform silicon ball.Synthetic 0.95g silicon ball, 145mL toluene, 12mL water and 3.4mL γ-methacryloxypropyl trimethoxy silane is mixed, at 40 DEG C, 700rpm/min stirs 22 hours, after centrifugal with whizzer, in 80 DEG C of vacuum drying ovens, be dried 3.5 hours, obtained hydrophobic silicon ball.
(2) the synthetic and sulfonation of the pik woods High Internal Phase Emulsion polymkeric substance of polymerization
First, the hydrophobic silicon ball of 0.95g, 2.9mL Vinylstyrene (DVB) and 0.035g Diisopropyl azodicarboxylate (AIBN); The hydrophobic silicon ball of 0.29g, 2.9mL Vinylstyrene (DVB), the 80(span80 of class of 0.18g department) and 0.035g Diisopropyl azodicarboxylate (AIBN); The hydrophobic silicon ball of 0.29g, 2.9mL Vinylstyrene (DVB), the 80(span80 of class of 0.59g department) and 0.035g Diisopropyl azodicarboxylate (AIBN) three series prepare respectively as oil phase, then, 0.035g Potassium Persulphate, 0.075g potassium sulfate and 0.19g sodium p styrene sulfonate (SSS) add in 16.5g deionized water as water, finally under high-speed stirring, water dropwise adds in oil phase, after 10-20 minute, it is prepared into respectively to stable pik woods High Internal Phase Emulsion.It is kept carrying out for 18-24 hour thermal-initiated polymerization reaction at 60-65 DEG C.The polymkeric substance obtaining respectively extracts 23 hours by acetone Soxhlet at 70 DEG C, and last pik woods high internal phase polymeric is 30 DEG C of vacuum-dryings.
Respectively the vitriol oil of the pik woods high internal phase polymeric obtaining and 98% mass ratio is reacted 12 hours at 70 DEG C, then filter, with washed with de-ionized water repeatedly until sulfuric acid clean, finally the oven drying of 80 DEG C 3 hours, obtain having their called after PDVB-SSS-X-SO of acidic polymer solid acid of porous
3h (X represents the volume of Si Ban 80) and PDVB-SSS-X-HF-SO
3h represents to have used hydrofluoric acid clean before sulfonation.
2, catalytic performance analytical test
(1) pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the productive rate of 5 hydroxymethyl furfural according to result.
Pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0-HF-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the product of 5 hydroxymethyl furfural according to result.
Result shows: PDVB-SSS-0-SO
3the productive rate 18.9% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0-HF-SO
3the productive rate 20.6% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0-HF-SO
3h catalytic effect is apparently higher than PDVB-SSS-0-SO
3h.
(2) pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0.19-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the productive rate of 5 hydroxymethyl furfural according to result.
Pre-treatment at present 120 DEG C of 0.1g Mierocrystalline cellulose and 2g 1-ethyl-3-methylimidazole villaumite ionic liquid 30 minutes, then at the PDVB-SSS-0.59-SO that adds 40mg in reaction vessel
3h, is reacting 2 hours.Add in reactor with a small amount of deionized water, then use brown volumetric flask constant volume, with the content of the synthetic 5 hydroxymethyl furfural of high performance liquid phase instrument analysis, and calculate the product of 5 hydroxymethyl furfural according to result.
Result shows: PDVB-SSS-0.19-SO
3the productive rate 29.6% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0.59-SO
3the productive rate 15.5% of the 5 hydroxymethyl furfural that H catalyse cellulose obtains, PDVB-SSS-0.19-SO
3h catalytic effect is apparently higher than PDVB-SSS-0.59-SO
3h.
Claims (5)
1. a method for macropore solid acid catalyst is prepared in pickering emulsion polymerization, it is characterized in that carrying out according to following step:
(1) the synthetic and silicon ball of silicon ball is hydrophobic modified
Tetraethoxy (TEOS) is added to CH
3cH
2oH and H
2in the aqueous solution of O, add inside subsequently the NH of 22 ~ 25% mass ratioes
3h
2o stirs 1-1.5 hour with 600 ~ 800rpm/min at 30 DEG C, centrifugal by whizzer after, in 60 ~ 80 DEG C of vacuum drying ovens dry 3 ~ 4 hours, obtained uniform silicon ball;
Synthetic silicon ball, toluene, water and γ-methacryloxypropyl trimethoxy silane (KH-570) are mixed, at 40 DEG C, stir 20 ~ 24 hours, after centrifugal by whizzer, in 60 ~ 80 DEG C of vacuum drying ovens, be dried 3 ~ 4 hours, obtained hydrophobic silicon ball;
(2) the synthetic and sulfonation of the pik woods High Internal Phase Emulsion polymkeric substance of polymerization
First, hydrophobic silicon ball, Vinylstyrene (DVB), the 80(span80 of class of department) and Diisopropyl azodicarboxylate (AIBN) prepare as oil phase in a series of ratios, then, Potassium Persulphate, potassium sulfate and sodium p styrene sulfonate (SSS) add in deionized water as water, finally under stirring with 900 ~ 1100rpm/min, water dropwise adds in oil phase, after 10 ~ 20 minutes, is prepared into stable pik woods High Internal Phase Emulsion; It is kept carrying out for 18 ~ 24 hours thermal-initiated polymerization reaction at 60 ~ 65 DEG C; The polymkeric substance obtaining extracts 20 ~ 24 hours by acetone Soxhlet at 60 ~ 80 DEG C, and last pik woods high internal phase polymeric is 25 ~ 30 DEG C of vacuum-dryings;
(3) vitriol oil of the pik woods high internal phase polymeric obtaining and 98% mass ratio is reacted 10 ~ 12 hours at 60 ~ 70 DEG C, then filter, repeatedly until sulfuric acid is cleaned, finally, the oven drying of 60 ~ 80 DEG C 3 ~ 4 hours, obtain the eurypyloue solid acid catalyst of tool by washed with de-ionized water.
2. the method for macropore solid acid catalyst is prepared in a kind of pickering emulsion polymerization according to claim 1, it is characterized in that wherein Vinylstyrene, the NH described in step (1)
3h
2o, CH
3cH
2oH, H
2o volume ratio is 5.8 ~ 6: 3 ~ 3.14: 85 ~ 90: 9 ~ 11.
3. the method for macropore solid acid catalyst is prepared in a kind of pickering emulsion polymerization according to claim 1, it is characterized in that wherein the synthetic silicon ball described in step (1), toluene, water and-methacryloxypropyl trimethoxy silane blending ratio is 0.9 ~ 1: 140 ~ 150: 8 ~ 15: 3.2 ~ 3.5(g/mL/mL/mL).
4. the method for macropore solid acid catalyst is prepared in a kind of pickering emulsion polymerization according to claim 1, the content ratio of mixture that it is characterized in that each monomer of hydrophobic silicon ball, Vinylstyrene, class of department 80 and Diisopropyl azodicarboxylate in the oil phase described in step (2) wherein has three groups, is respectively 0.9 ~ 1: 2.8 ~ 3: 0: 0.03 ~ 0.04 (g/mL/mL/g); 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).
5. the method for macropore solid acid catalyst is prepared in a kind of pickering emulsion polymerization according to claim 1, it is characterized in that wherein the deionized water described in step (2), Potassium Persulphate, 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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