CN104707653A - Novel polystyrene sulfonate-silicon oxide hybrid solid acid catalyst and preparation method thereof - Google Patents
Novel polystyrene sulfonate-silicon oxide hybrid solid acid catalyst and preparation method thereof Download PDFInfo
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- CN104707653A CN104707653A CN201310688928.9A CN201310688928A CN104707653A CN 104707653 A CN104707653 A CN 104707653A CN 201310688928 A CN201310688928 A CN 201310688928A CN 104707653 A CN104707653 A CN 104707653A
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Abstract
The invention relates to a polystyrene sulfonate-silicon oxide hybrid solid acid catalyst and a preparation method thereof. Specifically, sulfonic acid functionalized polystyrene-silicon oxide composite nano hollow spheres comprise polystyrene sulfonate and silicon oxide [polystyrene:silicon oxide=(5-50 wt%):(50-95 wt%)], and has a hollow sphere morphology; the acid content is in a range of 0.5-3.0 mmol/g H<+>, the specific surface area is 50-600 m<2>/g, and the pore volume is 0.1-0.4 cm<3>/g. The preparation method comprises the following specific preparation steps: in an alkaline system, with a cationic surfactant as a structure-directing agent, polystyrene as a co-template, and sodium silicate (Na2SiO3) or tetramethyl orthosilicate (TMOS) or tetraethoxysilane (TEOS) as an inorganic silicon source, stirring, filtering, and drying to obtain the polystyrene-silicon oxide nano hollow spheres; and carrying out a reaction of the obtained polystyrene-silicon oxide nano hollow spheres with a sulfonation reagent, filtering, and drying to finally obtain the polystyrene sulfonate-silicon oxide hybrid solid acid catalyst. The method has a few of steps, and the use time is short.
Description
Technical field
The present invention relates to polystyrene sulfonate-silica hydridization solid acid catalyst and preparation method, specifically a kind of sulfonic acid funtionalized polystyrene-silica compound nano-hollow sphere.
Background technology
The liquid mineral acid such as sulfuric acid, nitric acid, hydroiodic acid are conventional commercial acid catalyst, but in using, etching apparatus, product and catalyst separation difficulty and a large amount of spent acid produce and cause serious pollution to environment, and therefore the solid acid catalyst of development of new is paid close attention at present widely.Up to the present have developed miscellaneous solid acid catalyst as zeolite molecular sieve, heteropoly acid etc., be wherein much also applied in industrial production.Wherein cationic ion-exchange resin is the widely used solid acid catalyst of a class, but its specific area is lower and most active neutral is embedded in the polymer, because its swellability is bad in many solvents, reactant is difficult to be diffused into these activated centres, cause its activity not to be very high, its heat endurance is not high simultaneously also also limit its application to a certain extent.(Chemical Reviews, nineteen ninety-five, the 95th volume, 559-614 page; Journal of Molecular Ctalysis A:Chmical, 2002,182-183 rolled up, 439-445 page; Green Chemistry, 2010, the 95th volume, 1383-1391 page; Green Chemistry, 2010, the 12nd volume, 1981-1989 page; ChemicalCoumunications, 2009,4708-4710 page; Acs Ctalysis, 2011, the 1st volume, 674-681 page; Jounal of American Chemical Society, 2005, the 127th volume, 1924-1932 page).
Porous oxidation silicon materials get more and more people's extensive concerning due to its high mechanical strength, heat endurance and high-specific surface area.In porous oxidation silicon materials, assemble polymer prepare organic-inorganic hybrid nanomaterials and the Dominant Facies of polymer and porous oxidation silicon materials can be combined, arouse widespread concern in recent years.The method preparing this composite conventional mainly contains physical absorption, the method such as chemical modification and in-situ polymerization.But traditional preparation method is difficult to the composition and the pattern that control material, and the content of polymer is not high.The advantages such as it is short that the nano material with hollow ball structure has mass transfer path, and activated centre degree of exposure is high, have important application prospect at catalytic field.But the preparation at present with the polymer-silica hybrid material of hollow ball structure remains the difficult point of Material Field (Angewandte ChemieInternational Edition, the 45th volume, 3216-3251 page in 2006; Jounal of AmericanChemical Society, 2005, the 127th volume, 1924-1932 page; Jounal of AmericanChemical Society, calendar year 2001, the 123rd volume, 7497-7505 page; Macromolecules, 1998, the 31st volume, 592-601 page; Angewandte Chemie International Edition, 2005, the 44th volume, 6727-6730 page Chemistry of Materials, the 22nd year, 1309-1317 page in 2010).
Summary of the invention
The present invention relates to a kind of novel polystyrene sulfonate-silica hydridization solid acid catalyst and preparation method.Method of the present invention effectively can overcome the shortcomings such as the process complexity in existing technology of preparing, length consuming time, composition structure adjustment difficulty.The polystyrene sulfonate that simultaneously the present invention relates to-silica hydridization solid acid catalyst: described catalyst consist of polystyrene sulfonate and silica;
Described polystyrene: silica consists of (5-50wt%): (50-95wt%);
Described solid acid catalyst has hollow ball pattern;
The acid amount of described catalyst is at 0.5-3.0mmol/g H
+between, specific area is at 50-600m
2/ g, pore volume 0.1-0.4cm
3/ g.
The preparation method that the present invention relates to is as follows:
In alkaline solution, taking cationic surfactant as structure directing agent, with polystyrene (PS) for being total to template, adding inorganic silicon source, through stirring, filtering, dry, obtain polystyrene-monox nanometer hollow ball; The polystyrene obtained-monox nanometer hollow ball and sulfonated reagent are reacted, after filtration, drying finally obtains polystyrene sulfonate-silica hydridization solid acid catalyst.
Described cationic surfactant is quaternary amine salt form surfactant.
Described quaternary amine salt form surfactant is long chain alkane quaternary ammonium salt cationic surfactant: C
ntMAX, n=10-22, X=Br
-, Cl
-or OH
-; Comprise: the one in DTAC, softex kw or Cetyltrimethylammonium bromide.
In described alkaline system, alkaline solution is the one in concentrated ammonia liquor or sodium hydroxide solution.
Described inorganic silicon source presoma is sodium metasilicate (Na
2siO
3) or methyl silicate (TMOS) or ethyl orthosilicate (TEOS).
Described solution is second alcohol and water.
Sulfonated reagent is the one in the concentrated sulfuric acid and chlorosulfonic acid.
The mass ratio of described each component is: PS: cationic surfactant: inorganic silicon source presoma: water: ethanol=0.2-2:0.5-1.4:0.05-1:200-800:50-300.
10. preparation method according to claim 2, is characterized in that: between solution ph to 9-12, and in building-up process, temperature is 30 DEG C-100 DEG C, mixing time 2-12h, and crystallization temperature is 80 DEG C-120 DEG C.
Specifically can operate as follows:
1) preparation of the template aqueous solution: PS and quaternary amine salt form surfactant (as CTAB) are dissolved in deionized water and ethanol, PS ball and cationic surfactant are uniformly dispersed in system.
2) preparation of core-shell structure copolymer nano material: under agitation, adds NH in above-mentioned solution
3.H
2o solution or sodium hydroxide solution, add silicon source subsequently, and in building-up process, temperature is 30 DEG C-100 DEG C, mixing time 2-12h;
3) crystallization: step (2) is stirred the product crystallization 6-36h at 80 DEG C-120 DEG C after certain hour;
4) dry: by the product suction filtration of step (3), with water, ethanol washing, drying at room temperature;
5) removed template method: reflux the material after solvent process in the ethanolic solution 100-300mL containing concentrated hydrochloric acid 6-24h.
6) dry: by the product suction filtration of step (5), with water, ethanol washing, drying at room temperature;
7) sulfonating reaction: the product of step (6) and sulfonated reagent are reacted 1-12h.
8) dry: after the product massive laundering of step (7) to filtrate is become neutrality, to obtain product of the present invention by drying at room temperature after ethanol washing, filtration.
Preparation method's tool of the present invention has the following advantages:
1. materials synthesis takes the method for sulfonating reaction, simple, and productive rate is higher, is suitable for large-scale industrial production;
2. the amount by changing inorganic silicon source can realize the continuously adjustabe of Nanoparticle Size and outer wall thickness;
3. reaction temperature is lower, less energy consumption;
Material tool prepared by the present invention has the following advantages:
1. the material of preparation has good mechanical stability, heat endurance and acid catalyzed reaction activity;
2. the homogeneous and good dispersion of material particle size of preparation;
3. the material of preparation all has large specific area and pore volume, and high storage capacity, bio-compatibility are good, shell wall has inside and outside mesoporous;
4. the material prepared is that the polymer of silica and sulfonic acid funtionalized is composited, and the compound tool of this uniqueness has the following advantages: silica provides a kind of mesoporous carrier and polymer is born functional, combines silica and polymer advantage separately.
5. the wall thickness size of the material outer layer shell wall of preparation facilitates adjustable, has unique catalytic property;
6. the material outer layer of preparation is mesopore silicon oxide, and the mode by chemical modification introduces other functional group, can use as multifunction catalyst.
Accompanying drawing explanation
Fig. 1. for gained in embodiment 1 has the transmission electron microscope of the nano material of hollow ball spherical structure (TEM) photo;
Fig. 2. for gained in embodiment 2 has the TEM photo of the nano material of hollow ball spherical structure;
Fig. 3. for gained in embodiment 3 has the TEM photo of the nano material of hollow ball spherical structure;
Fig. 4. for gained in embodiment 4 has the TEM photo of the nano material of hollow ball spherical structure;
Fig. 5. for gained in embodiment 5 has the TEM photo of the nano material of hollow ball spherical structure;
Fig. 6. be the catalytic performance of products obtained therefrom in embodiment 1-3 in laurate and ethyl esterification react: 1-3 corresponds respectively to products obtained therefrom in example 1-3, and A is commercial ion exchange resin.
Fig. 7. be the catalytic performance of products obtained therefrom in laurate and ethyl esterification react in embodiment 4 and 5: 4 and 5 correspond respectively to products obtained therefrom in example 4 and 5, and A is commercial ion exchange resin.
Detailed description of the invention
In order to further illustrate the present invention, enumerate following embodiment, but it does not limit the invention scope that each accessory claim defines.
Embodiment 1
Under 50 DEG C of stirring conditions, 0.20g CTAB and 0.10g PS is scattered in 60mL deionized water and ethanolic solution, in backward solution, adds NH
3.H
2o regulates the pH value of solution, adds 3mmol TEOS after stirring, continues to stir 3h, 100 DEG C of crystallization 12h.Product after filtration, washing, after drying, with being dissolved with the ethanol solution of concentrated hydrochloric acid in 70 DEG C of extraction 12h; Product after filtration, washing, after drying, obtain white calomel mercurous chloride end.Sample characterizes through TEM and turns out to be hollow nano-sphere.At 0 DEG C, above-mentioned material is mixed with chlorosulfonic acid, return to room temperature after stirring 12h, wash by massive laundering, be washed till after filtrate becomes neutrality and wash with ethanol again, after filtration, drying, obtain faint yellow lightweight powder.TEM result shows that the product obtained is the nano material of hollow ball structure, uniform particle diameter, good dispersion, and the overall size of the hollow ball nano particle obtained is 530nm, outer wall thickness 110nm.BET specific surface area after sulfonation is 549.7m
2/ g; Pore volume is 0.55cm
3/ g; Acid amount is 1.50mmol H
+/ g.(Fig. 1)
Embodiment 2
Adopt the preparation process of embodiment 1, be with its difference, the quality of the PS added is 0.15g.Finally obtain faint yellow lightweight powder.Characterizing method is the same.TEM result shows that the product obtained is the nano material of hollow ball structure, uniform particle diameter, good dispersion, and the overall size of the hollow ball nano particle obtained is 410nm, outer wall thickness 80nm.BET specific surface area after sulfonation is 338.6m
2/ g; Pore volume is 0.32cm
3/ g; Acid amount is 1.65mmol H
+/ g.(Fig. 2)
Embodiment 3
Adopt the preparation process of embodiment 1, be with its difference, the quality of the PS added is 0.20g.Finally obtain faint yellow lightweight powder.Characterizing method is the same.TEM result shows that the product obtained is the nano material of hollow ball structure, uniform particle diameter, good dispersion, and the overall size of the hollow ball nano particle obtained is 500nm, outer wall thickness 110nm.BET specific surface area after sulfonation is 270.2m
2/ g; Pore volume is 0.28cm
3/ g; Acid amount is 1.8mmol H
+/ g.(Fig. 3)
Embodiment 4
Adopt the preparation process of embodiment 2, be with its difference, the amount in the silicon source added is 3.3mmol.Characterizing method is the same.TEM result shows that the product obtained is the nano material of hollow ball structure, uniform particle diameter, good dispersion, and the overall size of the hollow ball nano particle obtained is 360nm, outer wall thickness 58nm.BET specific surface area after sulfonation is 164.4m
2/ g; Pore volume is 0.21cm
3/ g; Acid amount is 1.5mmol H
+/ g.(Fig. 4)
Embodiment 5
Adopt the preparation process of embodiment 4, be with its difference, the quality of the PS added is 0.20g.Characterizing method is the same.TEM result shows that the product obtained is the nano material of hollow ball structure, uniform particle diameter, good dispersion, and the overall size of the hollow ball nano particle obtained is 320nm, outer wall thickness 50nm.BET specific surface area after sulfonation is 128m
2/ g; Pore volume is 0.14cm
3/ g; Acid amount is 1.9mmol H
+/ g.(Fig. 5)
The present invention relates to organic-inorganic hybrid nanomaterials, specifically a kind of polystyrene sulfonate-silica hydridization solid acid catalyst.Consist of polystyrene sulfonate and silica [polystyrene: silica is (5-50wt%): (50-95wt%); There is hollow ball pattern; Acid amount is at 0.5-3.0mmol/g H
+between, specific area is at 50-600m
2/ g, pore volume 0.1-0.4cm
3/ g.Under alkaline system, with cationic surfactant (quaternary amine salt form) for structure directing agent, with PS ball for being total to template, synthetic polystyrene-silica hybrid material, by sulfonation, washing, filter, dry, obtain polystyrene sulfonate-silica hydridization solid acid catalyst.This synthetic method step is few, and the used time is short, and material monolithic acid amount is high, has large specific area and pore volume and high heat endurance; The plurality of advantages such as grain graininess is homogeneous, good dispersion.Compare with commercialization cationic ion-exchange resin Amberlyst-15 and there is high catalytic activity (as shown in fig. 6-7.Fig. 6 and Fig. 7 is respectively the catalytic activity in the esterification of laurate and ethanol of gained solid acid catalyst in this example, and as shown in the figure, this example gained solid acid catalyst all shows the catalytic activity higher than business-like cationic ion-exchange resin).
Claims (10)
1. polystyrene sulfonate-silica hydridization solid acid catalyst, is characterized in that:
Described catalyst consist of polystyrene sulfonate and silica;
Described polystyrene: silica consists of (5-50wt%): (50-95wt%);
Described solid acid catalyst has hollow ball pattern;
The acid amount of described catalyst is at 0.5-3.0mmol/g H
+between, specific area is at 50-600m
2/ g, pore volume 0.1-0.4cm
3/ g.
2. a preparation method for polystyrene sulfonate-silica hydridization solid acid catalyst, is characterized in that:
In alkaline solution, taking cationic surfactant as structure directing agent, with polystyrene (PS) for being total to template, adding inorganic silicon source, through stirring, filtering, dry, obtain polystyrene-monox nanometer hollow ball; The polystyrene obtained-monox nanometer hollow ball and sulfonated reagent are reacted, after filtration, drying finally obtains polystyrene sulfonate-silica hydridization solid acid catalyst.
3. preparation method according to claim 2, is characterized in that: described cationic surfactant is quaternary amine salt form surfactant.
4. preparation method according to claim 3, is characterized in that: described quaternary amine salt form surfactant is long chain alkane quaternary ammonium salt cationic surfactant: C
ntMAX, n=10-22, X=Br
-, Cl
-or OH
-; Comprise: the one in DTAC, softex kw or Cetyltrimethylammonium bromide.
5. preparation method according to claim 2, is characterized in that: in described alkaline system, and alkaline solution is the one in concentrated ammonia liquor or sodium hydroxide solution.
6. preparation method according to claim 2, is characterized in that: described inorganic silicon source presoma is sodium metasilicate (Na
2siO
3) or methyl silicate (TMOS) or ethyl orthosilicate (TEOS).
7. preparation method according to claim 2, is characterized in that: described solution is second alcohol and water.
8. preparation method according to claim 2, is characterized in that: sulfonated reagent is the one in the concentrated sulfuric acid and chlorosulfonic acid.
9. preparation method according to claim 2, is characterized in that: the mass ratio of described each component is: PS: cationic surfactant: inorganic silicon source presoma: water: ethanol=0.2-2:0.5-1.4:0.05-1:200-800:50-300.
10. preparation method according to claim 2, is characterized in that: between solution ph to 9-12, and in building-up process, temperature is 30 DEG C-100 DEG C, mixing time 2-12h, and crystallization temperature is 80 DEG C-120 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134104A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108479860A (en) * | 2018-03-15 | 2018-09-04 | 厦门大学 | A kind of sulfonated polystyrene@mesoporous silicon dioxide micro-spheres and preparation method thereof with yolk-shell structure |
| CN115888825A (en) * | 2022-10-11 | 2023-04-04 | 江苏全邦材料科技有限公司 | Bisphenol A synthetic composite resin catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| CN103387717A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Organic/inorganic composite hollow microspheres, and preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| CN103387717A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Organic/inorganic composite hollow microspheres, and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134104A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108134104B (en) * | 2017-12-26 | 2020-05-12 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108479860A (en) * | 2018-03-15 | 2018-09-04 | 厦门大学 | A kind of sulfonated polystyrene@mesoporous silicon dioxide micro-spheres and preparation method thereof with yolk-shell structure |
| CN108479860B (en) * | 2018-03-15 | 2020-05-08 | 厦门大学 | Sulfonated polystyrene @ mesoporous silica microsphere with yolk-shell structure and preparation method thereof |
| CN115888825A (en) * | 2022-10-11 | 2023-04-04 | 江苏全邦材料科技有限公司 | Bisphenol A synthetic composite resin catalyst and preparation method thereof |
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