CN104258906A - Nano porous fixed acid catalyst with organic frame and synthesis method thereof - Google Patents
Nano porous fixed acid catalyst with organic frame and synthesis method thereof Download PDFInfo
- Publication number
- CN104258906A CN104258906A CN201410427035.3A CN201410427035A CN104258906A CN 104258906 A CN104258906 A CN 104258906A CN 201410427035 A CN201410427035 A CN 201410427035A CN 104258906 A CN104258906 A CN 104258906A
- Authority
- CN
- China
- Prior art keywords
- polydivinylbenezene
- catalyst
- described step
- solvent
- acid catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a nano porous fixed acid catalyst with an organic frame and a synthesis method thereof. The catalyst comprises a poly(divinyl benzene) basic frame and a sulfonic active site. The solid acid catalyst has the advantages of capability for swelling, large specific area, high sulfonic group content, stable frame structure, and high catalytic activity. The disclosed catalyst and synthesis method thereof overcome the shortages of bad organic frame stability and low specific area in the conventional solid acid catalysts.
Description
Technical field
The invention belongs to technical field of material chemistry, relate to a kind of catalyst, particularly a kind of nanoporous organic backbone fixed acid Catalysts and its preparation method.
Background technology
Recent years, development solid acid catalyst along with chemical industry obtains to be studied widely, especially play a part very important in petrochemical industry and field of fine chemical, traditional acid catalyst has zeolite molecular sieve, sulphided metal oxides, the mesoporous material of acid functionalization, heteropoly acid etc., but its shortcoming as: hydrophilic skeleton structure, the aperture restriction etc. of zeolitic material have impact on inorganic solid acid material and applies more widely.Compared with the acid catalyst of conventional inorganic skeleton, the solid-acid material of pure organic backbone with the skeleton hydrophilicity and hydrophobicity of its uniqueness, simply and easily functionalization process, good catalytic performance and be subject to studying more and more widely.
United States Patent (USP): B01J31/10; B01J47/00; C07C37/20 etc. disclose a kind of storng-acid cation exchange resin, its skeleton has divinylbenzene and styrol copolymer, active function groups is sulfonate radical, as a kind of novel organic backbone solid-acid material, hydrophobic skeleton structure and high acid site content make this material be widely used in the field such as acid catalyzed reaction and ion-exchange, comprise esterification, ester exchange, etherificate, achieve good effect (J.Catal.2008,254,205.), now by industrialization, in commercial Application, occupy very important position.But its low specific surface area, deficient pore structure and poor stability, to the adverse influence of catalytic reaction, poor can limit it with the skeleton structure of less stable and apply widely.
Summary of the invention
The object of this invention is to provide a kind of novel swellable, bigger serface, high sulfonate radical content has the synthetic method of the novel solid acid of stabilization of bony shelf structure and high catalytic activity simultaneously, and to overcome traditional organic backbone poor stability, specific area is low, etc. shortcoming.
For achieving the above object, the present invention takes following technical proposals to realize:
The invention provides a kind of nanoporous organic backbone fixed acid catalyst, employing polydivinylbenezene is basic framework, and sulfonate radical is activated centre.
Preferably, the specific area of polydivinylbenezene is 500-700m
2/ g, average pore size is 5-32nm, and pore volume is 0.5-1.35ml/g.
Preferred, the specific area of polydivinylbenezene is 700m2/g, and average pore size is 25nm, and pore volume is 1.25ml/g.
Preferably, the specific area of the polydivinylbenezene after sulfonation is 280-550m
2/ g, average pore size is 6-34nm, and pore volume is 0.3-0.9ml/g.
Preferred, the specific area of the polydivinylbenezene after sulfonation is 350-500m2/g, and average pore size is 15-23nm, and pore volume is 0.4-0.9ml/g.
The present invention also provides a kind of preparation method of nanoporous organic backbone fixed acid catalyst, comprises the following steps:
A. be monomer with divinylbenzene, azodiisobutyronitrile is initator, is had the mesoporous polydivinylbenezene blocks of solid of bigger serface by the method synthesis of solvent heat;
B. take chloroform as solvent, the concentrated sulfuric acid is sulfonated reagent, by the sulfonation of polydivinylbenezene blocks of solid under heated reflux condition, obtains the swollen sulfonated porous polydivinylbenezene material of powdered soluble;
C. the sulfonated porous polydivinylbenezene material obtained in step b is carried out drying, nanoporous organic backbone fixed acid catalyst.
Further, in described step a, solvent is oxolane, ethyl acetate, methyl acetate, one or more in DMF.
Preferably, in described step a, solvent is oxolane.
Preferably, in described step a, synthesis temperature is 75-150 DEG C, preferred, and in step a, synthesis temperature is 100-150 DEG C.
Preferably, in described step a, synthesis pressure is 0.5-1.35MP.
Further, in described step b, sulfonate radical content is 2.1 ~ 3.4mmol/g, and hydrogen ion exchange capacity is 2.2 ~ 3.8mmol/g.
Further, in described step c, baking temperature is 80 DEG C.
Compared with prior art, the present invention has the following advantages:
The resin material that the present invention is obtained by divinyl benzene polymer, greatly improve than the degree of cross linking with traditional resin-phase, and then the stability of material also improves greatly, there is large specific area and abundant pore structure simultaneously, then can make material while maintenance high stability by first swelling rear sulfonation, sulfonation obtains more abundant; While keeping Large ratio surface sum pore structure, improve the stability of sulfonated products, thus obtain the novel solid acid material of high activity center content.Model reaction also proves that this material list reveals the catalytic activity higher than ion exchange resin and catalytic stability, very meaningful to the development of exploitation organic backbone solid-acid material.
The inventive method is simply effective, utilizes the feature of swellability can successfully introduce a large amount of sulfonate radicals.
The mesoporous polydivinylbenezene of sulfonic acid funtionalized of the present invention has large specific area (523m2/g).
The mesoporous polydivinylbenezene material of sulfonation of the present invention has higher sulfonate radical content (2.45mmol/g).
The mesoporous polydivinylbenezene of sulfonic acid funtionalized of the present invention has stable skeleton structure (595 DEG C) and stable acid site (320 DEG C).
The mesoporous polydivinylbenezene of sulfonic acid funtionalized of the present invention shows good catalytic activity and regenerability in catalytic esterification and F-K reaction, and after recycling 5 times, activity reduces 11.3%.
Detailed description of the invention
Illustrative example below, illustrates in the present invention to have efficient stable structure, high-specific surface area, the synthetic method of the novel solid acid material of high sulfonate radical content.
In embodiment, sample name is divided into two parts: PDVB represents mesoporous polydivinylbenezene, and "-SO3H " represents the mesoporous polydivinylbenezene material after sulfonate radical functionalization.
Embodiment 1
First carry out synthesising mesoporous polydivinylbenezene material with oxolane and water for mixed solvent, be PDVB.
2g DVB monomer is joined and closes 0.03-0.05g azobisisobutyronitrile and 10-20 milliliter oxolane, in the mixed solvent of 1-2 ml water, > is stirred after 3 hours under normal temperature and pressure, the heat treatment of 75-150 DEG C water was taken out after 1-2 days, uncap, room temperature is volatilized dry solvent, can obtain high-specific surface area, enrich the polydivinylbenezene material (PDVB) of meso-hole structure.
Embodiment 2
Select carrene/toluene/carbon tetrachloride etc. to be solvent, the concentrated sulfuric acid is that sulfonated reagent carries out sulfonating reaction.
2-3g PDVB is ground to form superfines, degassed process 10h under 100-150 DEG C of condition of nitrogen gas; Swelling process: add in excessive solvent by 2.0g PDVB block, PDVB material occurs rapidly swelling, and PDVB bursts into fritter very soon, swells rapidly with volume simultaneously.
Get 30mL chloroform, 70mL oleum, after stirring, add above-mentioned PDVB, strong stirring, temperature is elevated to room temperature sulfonation 24h, terminate reaction, product filters, and dioxane washs, and is washed to neutrality, 80 DEG C of dryings, wash after sulfuric acid activated 4 hours with 0.1M that massive laundering is to neutral, dry, stand-by.
Embodiment 3
Catalytic performance test and the contrast with conventional catalyst material thereof
The esterification condition of acetic acid and cyclohexanol: 0.2g catalyst, 11.5mL cyclohexanol, 17.5mL glacial acetic acid mixes rear 100 DEG C of reaction 5h to be terminated, and dodecane is interior mark.
The esterification condition of n-caproic acid and ethanol: 0.3g catalyst, 6.26mL n-caproic acid, 11.67mL ethanol mixes rear 80 DEG C of reaction 5h to be terminated, and dodecane is interior mark.
The esterification condition of dodecoic acid and ethanol: 0.15g catalyst, 4mmol dodecoic acid, 50mmol ethanol mixes rear 70 DEG C of reaction 5h to be terminated, and dodecane is interior mark.
F-K reaction: 0.3g catalyst, 5.5mL methyl phenyl ethers anisole, 0.71mL chloroacetic chloride mixes rear 60 DEG C of reaction 5h to be terminated, and dodecane is interior mark.
Subordinate list 1 gives the catalytic activity of material in catalytic esterification and acylation reaction, can find out that this material shows good catalytic activity reaction conversion ratio to multiple acid catalyzed reaction and is followed successively by: 62.5,72.5,89.4,61.8%; In catalytic esterification, after recycling 5 times, activity reduces 11.3%, shows that this material has good power of regeneration and anti-poisoning ability.
Table 1 synthesizes the catalytic activity of sulfonate materials in esterification and acylation reaction.
a0.2g catalyst.
b0.1g catalyst.
c0.2g catalyst is recycled four times in catalysis ethyl cyclohexyl alcohol esterification.
dethyl cyclohexyl alcohol esterification.
en-caproic acid and ethyl esterification reaction.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; the Method and Technology content of above-mentioned announcement can be utilized to make possible variation and amendment to technical solution of the present invention; therefore; every content not departing from technical solution of the present invention, all belongs to the protection domain of technical solution of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification according to technical spirit of the present invention.
Claims (10)
1. a nanoporous organic backbone fixed acid catalyst, is characterized in that, employing polydivinylbenezene is basic framework, and sulfonate radical is activated centre.
2. catalyst according to claim 1, is characterized in that, the specific area of polydivinylbenezene is 500-700m
2/ g, average pore size is 5-32 nm, and pore volume is 0.5-1.35 ml/g.
3. catalyst according to claim 1, is characterized in that, the specific area of the polydivinylbenezene after sulfonation is 280-550m
2/ g, average pore size is 6-34 nm, and pore volume is 0.3-0.9 ml/g.
4. the preparation method of catalyst as claimed in claim 1, is characterized in that, comprise the following steps:
A. be monomer with divinylbenzene, azodiisobutyronitrile is initator, is had the mesoporous polydivinylbenezene blocks of solid of bigger serface by the method synthesis of solvent heat;
B. take chloroform as solvent, the concentrated sulfuric acid is sulfonated reagent, by the sulfonation of polydivinylbenezene blocks of solid under heated reflux condition, obtains the swollen sulfonated porous polydivinylbenezene material of powdered soluble;
C. the sulfonated porous polydivinylbenezene material obtained in step b is carried out drying, nanoporous organic backbone fixed acid catalyst.
5. method according to claim 4, is characterized in that, in described step a, solvent is oxolane, ethyl acetate, methyl acetate, one or more in DMF.
6. method according to claim 5, is characterized in that, in described step a, solvent is oxolane.
7. method according to claim 4, is characterized in that, in described step a, synthesis temperature is 75-150 DEG C.
8. method according to claim 4, is characterized in that, in described step a, synthesis pressure is 0.5-1.35MP.
9. method according to claim 4, is characterized in that, in described step b, sulfonate radical content is 2.1 ~ 3.4 mmol/g, and hydrogen ion exchange capacity is 2.2 ~ 3.8 mmol/g.
10. method according to claim 4, is characterized in that, in described step c, baking temperature is 80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410427035.3A CN104258906A (en) | 2014-08-27 | 2014-08-27 | Nano porous fixed acid catalyst with organic frame and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410427035.3A CN104258906A (en) | 2014-08-27 | 2014-08-27 | Nano porous fixed acid catalyst with organic frame and synthesis method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104258906A true CN104258906A (en) | 2015-01-07 |
Family
ID=52150554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410427035.3A Pending CN104258906A (en) | 2014-08-27 | 2014-08-27 | Nano porous fixed acid catalyst with organic frame and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104258906A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040297A (en) * | 2016-05-27 | 2016-10-26 | 河南工业大学 | Method for preparing hydrophobic solid organic-acid catalyst |
| CN106345435A (en) * | 2016-09-27 | 2017-01-25 | 华南理工大学 | Preparation method of metal-organic framework/polydivinylbenzene composite VOCs (Volatile Organic Chemicals) adsorbent |
| CN108410002A (en) * | 2018-03-23 | 2018-08-17 | 绍兴文理学院 | A kind of Performances of Novel Nano-Porous metre hole organic backbone solid alkali material |
| CN110483678A (en) * | 2019-07-19 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and its preparation method and application preparing isobide for sorb dehydration of alcohols |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788279A (en) * | 2014-01-21 | 2014-05-14 | 绍兴文理学院 | Super-hydrophobic aggregate type nano-porous solid alkali material and preparation method thereof |
| CN103819598A (en) * | 2014-02-11 | 2014-05-28 | 绍兴文理学院 | Nanometer porous and super-hydrophobic skeleton strong solid acid material and preparing method thereof |
-
2014
- 2014-08-27 CN CN201410427035.3A patent/CN104258906A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788279A (en) * | 2014-01-21 | 2014-05-14 | 绍兴文理学院 | Super-hydrophobic aggregate type nano-porous solid alkali material and preparation method thereof |
| CN103819598A (en) * | 2014-02-11 | 2014-05-28 | 绍兴文理学院 | Nanometer porous and super-hydrophobic skeleton strong solid acid material and preparing method thereof |
Non-Patent Citations (4)
| Title |
|---|
| FUJIAN LIU, ET AL.: "Design and synthesis of hydrophobic and stable mesoporous polymeric catalytic activities for biomass transformation", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| FUJIAN LIU, ET AL.: "High-temperature synthesis of magnetically active and SO3H-functionalized ordered ordered mesoporous carbon with good catalytic performance", 《CATALYSIS TODAY》 * |
| YONGLAI ZHANG, ET AL.: "Superhydrophobic nanoporous polymers as efficient adsorbents for organic compounds", 《NANO TODAY》 * |
| 刘福建: "高温水热，溶剂热法合成稳定多功能化的介孔材料", 《中国优秀博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040297A (en) * | 2016-05-27 | 2016-10-26 | 河南工业大学 | Method for preparing hydrophobic solid organic-acid catalyst |
| CN106345435A (en) * | 2016-09-27 | 2017-01-25 | 华南理工大学 | Preparation method of metal-organic framework/polydivinylbenzene composite VOCs (Volatile Organic Chemicals) adsorbent |
| CN108410002A (en) * | 2018-03-23 | 2018-08-17 | 绍兴文理学院 | A kind of Performances of Novel Nano-Porous metre hole organic backbone solid alkali material |
| CN110483678A (en) * | 2019-07-19 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and its preparation method and application preparing isobide for sorb dehydration of alcohols |
| CN110483678B (en) * | 2019-07-19 | 2021-09-14 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing isosorbide by dehydrating sorbitol and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102861611B (en) | Application of organic framework porous solid acid | |
| Liu et al. | Design and synthesis of hydrophobic and stable mesoporous polymeric solid acid with ultra strong acid strength and excellent catalytic activities for biomass transformation | |
| CN102626661B (en) | Strong-acid type polystyrene cation exchange resin as well as preparation method and application thereof | |
| CN103182324B (en) | Preparation method of hydrophobic organic framework solid base catalyst | |
| CN101274269B (en) | Adsorption resin with centralized pore diameter and large Micropore specific surface area and method for producing the same | |
| CN104258906A (en) | Nano porous fixed acid catalyst with organic frame and synthesis method thereof | |
| CN104248980B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN101961660B (en) | Porous hybrid-resin solid acid catalyst and preparation method thereof | |
| CN102942701B (en) | Phenolic hydroxyl group-containing ultrahigh cross-linked adsorption resin and preparation method and application thereof | |
| Tian et al. | A new sulfonic acid-functionalized organic polymer catalyst for the synthesis of biomass-derived alkyl levulinates | |
| CN111793176B (en) | Lignin-based hypercrosslinked polymer with hierarchical pore structure and preparation method and adsorption application thereof | |
| CN103819598A (en) | Nanometer porous and super-hydrophobic skeleton strong solid acid material and preparing method thereof | |
| CN104248987A (en) | Spherical montmorillonite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate | |
| CN101690885A (en) | 4-vinylpyridine absorbent resin and preparation method thereof | |
| CN104248993A (en) | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method | |
| Lei et al. | SO3H-functionalized porous organic polymer with amphiphilic and swelling properties: A highly efficient solid acid catalyst for organic transformations in water | |
| CN104525260A (en) | Polymeric solid acid catalyst for esterification reaction and preparation method thereof | |
| CN114349890B (en) | Ultrahigh crosslinked resin and preparation method and application thereof | |
| CN103788279A (en) | Super-hydrophobic aggregate type nano-porous solid alkali material and preparation method thereof | |
| CN104248984B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CA2293915C (en) | High surface area adsorbents and method of preparation | |
| CN108579803B (en) | Preparation method of ionic liquid loaded polymer porous microspheres | |
| CN113578383A (en) | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere | |
| CN110483678B (en) | Catalyst for preparing isosorbide by dehydrating sorbitol and preparation method and application thereof | |
| CN101927185A (en) | Preparation of macroporous strong-acid cation-exchange resin catalyst and use thereof in catalytic synthesis of methyl 2-keto-L-gulonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150107 |